Polymers containing complex hydrophobic groups

ABSTRACT

Water-soluble polymers are disclosed which comprise hydrophobic segments, each segment containing at least one hydrophobic group or comlex hydrophobic group covalently bonded to the polymer, wherein the polymer has an amount of complex hydrophobic groups sufficient to provide for enhanced thickening of aqueous solutions containing the polymer. These polymers provide superior thickening and leveling in aqueous systems through hydrophobic associations, and aid suspension of particulate materials in non-aqueous systems.

RELATED APPLICATIONS

This application is a division of prior U.S. application Ser. No.07/887,641 Filing Date May, 29, 1992 now U.S. Pat. No. 5,292,828.

The following are related, commonly assigned applications, filed on aneven date herewith:

U.S. patent application Ser. No. 07/887,647 filed May 29, 1992, now U.S.Pat. No. 5,292,843; U.S. patent application Ser. No. 07,887,646 filedMay 29, 1992; U.S. patent application Ser. No. 07/887,642 filed May 29,1992; U.S. patent application Ser. No. 07/887,673 filed May 29, 1992;U.S. patent application Ser. No. 07/887,672 filed May 29, 1992; U.S.patent application Ser. No. 07/887,645 filed May 29, 1992; U.S. patentapplication Ser. No. 07/887,648 filed May 29, 1992; U.S. patentapplication Ser. No. 07/887,643 filed May 29, 1992; U.S. patentapplication Ser. No. 07/887,644 filed May 29, 1992; and U S. patentapplication Ser. No. 07/887,671 filed May 29, 1992, now abandoned; allof which are incorporated herein by reference.

BRIEF SUMMARY OF THE INVENTION Technical Field

This invention relates to water-soluble polymers which comprisehydrophobic segments, each segment containing at least one hydrophobicgroup or complex hydrophobic group covalently bonded to the polymer,wherein the polymer has an amount of complex hydrophobic groupssufficient to provide for enhanced thickening of aqueous solutionscontaining the polymer.

BACKGROUND OF THE INVENTION

A great variety of polymeric materials, natural and synthetic, have beendisclosed to be useful thickening agents, yet only a few of thesematerials find commercial use today. Many of those which are usedcommercially, such as hydroxyethyl cellulose or methyl cellulose, do notprovide both the thickening power required as well as the flow andleveling desired in the formulation. Consequently, in order to meet themarket demands for improved paint formulations, it is important to finda new materials which will provide the above combination of properties.

DISCLOSURE OF THE INVENTION

This invention relates to water-soluble polymers which comprisehydrophobic segments, each segment containing at least one hydrophobicgroup or complex hydrophobic group covalently bonded to the polymer,wherein the polymer has an amount of complex hydrophobic groupssufficient to provide for enhanced thickening of aqueous solutionscontaining the polymer. The polymers can also have an amount ofbunching, defined as hydrophobic segments comprising at least twohydrophobic groups, complex hydrophobic groups or mixtures thereof,which can provide for enhanced thickening of aqueous solutionscontaining the polymer. Processes for the production and use of suchpolymers are also described.

DETAILED DESCRIPTION

It has been found that good thickening and leveling properties inwaterborne coatings can be achieved without tailor-making the polymericbackbone structure. Effective thickening and leveling properties can beintroduced into waterborne coating systems without the necessity ofproviding polymeric backbones of unique structures other than providingthose polymers with the capacity to be dissolved in water to the degreenecessary for the application at hand. It has been found that all thatis necessary to provide synthetic, water-soluble thickeners mostdesirable for use in waterborne coating systems is the introduction to awater-soluble polymeric backbone of special hydrophobic groups,hereinafter referred to as complex hydrophobes or complex hydrophobicgroups. One achieves through these complex hydrophobic groups aninteraction and interconnection of the various dissolved water-solublepolymers. This interaction and interconnection results in an associativecrosslinking of these polymers such that within the aqueous phase theyform a network resulting in a unique thickening action, and also provideextremely good flow and leveling properties. It is believed that theunique polymers of this invention provide good thickening and levelingproperties to a waterborne system by hydrophobic association.

The important features of hydrophobic association include: (a) noparticle-to-polymer interactions required for thickening to take place(for example, the polymers of this invention have the capacity ofthickening pure water); (b) interaction of the hydrophobic and complexhydrophobic groups provides a capacity to effectively crosslink thepolymers sufficiently to cause an increase in the viscosity and henceachieve the desired thickening characteristics; (c) under shearconditions, the viscosity of the aqueous phase of the waterborne systemscan decrease; and (d) upon removal of shear force, there is atime-dependent rebuilding of rheological properties. This timedependence provides the consequent good flow and levelingcharacteristics which are sought in waterborne coating systems.

As indicated above, hydrophobic association is based upon the existencewithin the aqueous phase of intermolecular associations between thehydrophobic and complex hydrophobic groups bonded to the water-solublepolymer. In the broadest characterization, hydrophobic association isintended to mean the approximate aggregation of at least two hydrophobicgroups, complex hydrophobic groups or mixtures serving to exclude waterat that proximity. Hydrophobic association can be looked at as acongregation of hydrophobic groups, complex hydrophobes or mixtureswhich locally excludes water. These hydrophobic groups associations aredynamic, molecular, hydrophobic associations, which occur in aqueoussolution. These associations occur only in abundance above a criticalconcentration, i.e., the critical micelle concentration, CMC. CMC can bedefined as the amount of hydrophobe or complex hydrophobe containingcompound which is required to saturate a solution at standardconditions, such that the addition of any more hydrophobe or complexhydrophobe containing compound will produce a phase separation on amolecular level resulting in the formation of micelle-like associations.As such, at a concentration above the CMC, the amount of free hydrophobeor complex hydrophobe containing compound, i.e., having unassociatedhydrophobes or complex hydrophobes, in solution will not increase. Thetime averaged, i.e., equilibrium, number and size of hydrophobicassociations are constant at constant conditions, such as temperature,concentration, ionic strength and the like. The duration of time that anindividual hydrophobic association exists is related to the (1) chemicalpotential of the hydrophobe and complex hydrophobe as compared to its(aqueous) environment and (2) static factors, such as the proximity ofone hydrophobe or complex hydrophobe to another, which aid and abet theapproach of two or more hydrophobes or complex hydrophobes to eachother. The chemical potential of the hydrophobe and complex hydrophobe,Δμ, can be roughly estimated by the equation: ##EQU1## wherein R is theuniversal gas constant; T is temperature in degrees Kelvin; V_(s) andV_(P) are the molar volumes of the solvent (water) and the hydrophobe orcomplex hydrophobe respectively; δ_(s) and δ_(P) are the solubilityparameters of the solvent (water) and hydrophobe or complex hydrophoberespectively; and x is the volume fraction concentration of hydrophobeor complex hydrophobe present. This chemical potential equation can bededuced from the theory of the solubility of liquids in liquids aspresented in The Solubility of Non-Electrolytes, by J. H. Hildebrand andR. L. Scott at page 253, published by Dover Publication, Inc., New York,N.Y. (1964). The more negative the value of Δμ, the stronger thepropensity to form and maintain hydrophobic associations. Thus, stronghydrophobic associations are possible where there is a large disparitybetween the molar volumes of the solvent (water) and the hydrophobe andcomplex hydrophobe, as well as a large difference between the solubilityparameters. Weak associations occur when only slight differences betweenthese two factors exist. When the chemical potential is zero orpositive, aggregation by hydrophobic association is not expected and thesystem is below critical micelle concentration, CMC. Indeed under suchconditions materials should be mutually soluble.

There is described herein novel polymeric structures with propertiesmaking them eminently suitable for use in aqueous and non-aqueouscompositions, while creating unique and useful properties and effectswhen so used. The polymers of this invention are characterized by havinghydrophobic and complex hydrophobic groups interbonded to thewater-soluble backbone. As a result, the polymer contains a mass of botha water-soluble polymer component, a complex hydrophobic component andoptionally a hydrophobic component that act separately from each otherbringing unique attributes to the total polymer.

The novel polymers of this invention provide a unique thickeningcapability in aqueous systems which is believed to stem from the unique,complex hydrophobic groups interbonded to the water-soluble backbone.These complex hydrophobic groups, which can be bunched, have the abilityto readily form hydrophobic associations in water, with hydrophobic andcomplex hydrophobic groups from other molecules of the polymer. Becausethe hydrophobic associations interconnect a number of polymers, there isa build-up of interlocking water-soluble polymer backbones achievedthrough this hydrophobic association. Such interlocking of hydrophobicand complex hydrophobic groups in hydrophobic associations causes adramatic increase in the apparent molecular weight of the polymerresulting in an increased viscosity of the aqueous medium.

Hydrophobic association applies to the polymers of this invention inaqueous systems and conceptually allows a great degree of freedom fromthe high degree of specificity in the definition of the particularpolymer backbone, while at the same time explains why the utilization ofcomplex hydrophobes provides unique theology to dilute aqueous solutionsof the polymers of this invention.

The implication of hydrophobic association is that the particularstructure of the polymeric backbone which generates water-solubility isnot critical to the performance of the polymer in the thickeningoperation other than providing hydrophilic quality to the molecule. Whatis critical is the placement of the complex hydrophobic groups in thepolymer so as to enhance bridging of polymer chain to polymer chainthereby achieving enhanced thickening in aqueous systems.

Because the polymers of this invention are believed to operate byhydrophobic association, it is inconsequential to the practice of thisinvention as to the particular structure of the polymeric backboneinvolved so long as it provides the water-soluble characteristics to thetotal polymer and at the same time provides the substrate for theattachment of complex hydrophobic groups. For purposes of thisinvention, polymers having a polymeric backbone containing urethaneunits which are used for thickening aqueous, emulsion polymer, latexcompositions are outside the scope of this invention.

The critical feature of the present invention is the provision in thewater-soluble polymer of hydrophobic segments in which the polymer hasat least one complex hydrophobic group. The hydrophobic segments canhave one or more hydrophobes thereby forming a bunch of hydrophobeswithin that hydrophobic segment. In particular, the hydrophobic andcomplex hydrophobic groups within a hydrophobe segment can be in closeassociation or proximity, preferably separated from each other by nomore than about 50, most preferably less than about 25, covalentlybonded, sequentially connected atoms, which can be sufficient to providefor enhanced thickening of aqueous solutions containing the polymerthrough the formation of intermolecular hydrophobic associations. Ahydrophobic segment is defined as that portion of the water-solublepolymer having at least one hydrophobic and/or complex hydrophobicgroup. Such segments serve the unique function of providing for thenucleation of extraordinarily strong intermolecular hydrophobicassociations when incorporated in an aqueous medium. The polymer maycontain up to a substantial proportion of hydrophobic segments havingbunched hydrophobic and complex hydrophobic groups. In anotherembodiment, essentially all the hydrophobic segments in thewater-soluble polymer can have bunched hydrophobic and complexhydrophobic groups.

The number of hydrophobic and complex hydrophobic groups per hydrophobicsegment required to provide optimum thickening efficiency can bedecreased by either increasing the molar volume of the hydrophobe orcomplex hydrophobe or by reducing its contribution to the solubilityparameter.

The polymer can preferably contain from about 2 to 25 hydrophobicsegments, and most preferably from about 4 to about 11 segments permolecule. The number of hydrophobic segments is not critical so long asa sufficient number of hydrophobe segments is provided to enable thegeneration of intermolecular hydrophobic associations when the polymeris in aqueous solution.

It is to be understood that the benefits of this invention can beachieved in many cases by a relatively low concentration of polymermolecules which contain complex hydrophobic groups of this invention inmixtures with polymer molecules which do not contain such complexhydrophobic groups.

The composition of the hydrophobic compounds from which the hydrophobesare derived is not critical so long as the hydrophobes provide a molarvolume contribution of greater than about 70 cubic centimeters per mole,and preferably greater than about 160 cubic centimeters per mole, andhaving a nominal contribution to the calculated solubility parameter ofless than about 9.5 (cal./cc)^(1/2), and preferably from about 6.5 toabout 9.0 (cal./cc)^(1/2). The molar volume and solubility contributionsof various hydrophobes are readily estimated from their structure usingmethods well described in the literature, as in "New Values Of TheSolubility Parameter From Vapor Pressure Data", by K. L. Hoy, Journal ofPaint Technology, Volume 482, 116 (1970); "Solubility Parameters ForFilm Formers" by H. Burrell, Official Digest, 726 (1955); "Molar VolumeAdditivity Of Polymers", by R. Kawai, Chemistry of High Polymers,(Japan), Volume 13, Page 139 to 147 (1956); and Properties of Polymers,by D. W. Van Krevelan Elsevier/North-Holland, Inc., New York, N.Y.,Chapter 7, 129 (1976).

                  TABLE 1                                                         ______________________________________                                        Calculated Molar Volumes and Solubility                                       Parameters for Selected Hydrophobes                                                                       Solubility                                                        Molar Volume,                                                                             Parameter                                         Hydrophobe      cc/mole     (cal/cc).sup.1/2                                  ______________________________________                                        n-pentyl         83.7       8.06                                              tolyl            90.1       9.04                                              ethylphenyls    105.6       8.95                                              n-propylphenyls 121.2       8.89                                              n-butylphenyls  136.7       8.84                                              n-phenylphenyls 152.3       8.80                                              isohexylphenyls 161.8       8.63                                              n-hexylphenyls  167.8       8.77                                              n-heptylphenyls 183.4       8.74                                              n-octylphenyls  198.9       8.72                                              isononylphenyls 208.5       8.26                                              n-nonylphenyls  214.5       8.70                                              n-decylphenyls  230.0       8.68                                              n-undecylphenyls                                                                              245.6       8.67                                              isododecylphenyls                                                                             255.1       8.34                                              n-dodecylphenyls                                                                              261.1       8.66                                              n-tetradecylphenyls                                                                           292.2       8.63                                              n-hexadecylphenyls                                                                            338.9       8.62                                              isooctadecylphenyls                                                                           348.5       8.21                                              ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Calculated Molar Volumes and Solubility                                       Parameters for Selected Biphobes of the Form:                                  ##STR1##                                                                                              Molar    Solubility                                                           Volume,  Parameter                                   R.sub.1   R.sub.2        cc/mole  (cal/cc).sup.1/2                            ______________________________________                                        n-nonylphenyl                                                                           methyl         289.6    8.72                                        n-nonylphenyl                                                                           ethyl          305.1    8.78                                        n-nonylphenyl                                                                           n-propyl       320.7    8.70                                        n-nonylphenyl                                                                           iso-propyl     320.7    8.60                                        n-nonylphenyl                                                                           n-butyl        336.3    8.69                                        n-nonylphenyl                                                                           iso-butyl      336.3    8.60                                        n-nonylphenyl                                                                           neo-butyl      336.3    8.47                                        n-nonylphenyl                                                                           n-pentyl       351.8    8.68                                        n-nonylphenyl                                                                           iso-pentyl     351.8    8.59                                        n-nonylphenyl                                                                           neo-pentyl     351.8    8.59                                        n-nonylphenyl                                                                           n-hexyl        367.4    8.67                                        n-nonylphenyl                                                                           iso-hexyl      367.4    8.58                                        n-nonylphenyl                                                                           neo-hexyl      367.4    8.58                                        n-nonylphenyl                                                                           n-heptyl       382.9    8.66                                        n-nonylphenyl                                                                           iso-heptyl     382.9    8.57                                        n-nonylphenyl                                                                           neo-heptyl     382.9    8.57                                        n-nonylphenyl                                                                           n-octyl        398.5    8.64                                        n-nonylphenyl                                                                           iso-octyl      398.5    8.56                                        n-nonylphenyl                                                                           neo-octyl      398.5    8.56                                        n-nonylphenyl                                                                           n-nonyl        414.0    8.62                                        n-nonylphenyl                                                                           iso-nonyl      414.0    8.55                                        n-nonylphenyl                                                                           neo-nonyl      414.0    8.55                                        n-nonylphenyl                                                                           n-decyl        429.6    8.60                                        n-nonylphenyl                                                                           iso-decyl      429.6    8.54                                        n-nonylphenyl                                                                           neo-decyl      429.6    8.54                                        n-nonylphenyl                                                                           linear and branched                                                 n-nonylphenyl                                                                           alkyls                                                              n-nonylphenyl                                                                           n-undecyl      445.1    8.58                                        n-nonylphenyl                                                                           iso-undecyl    445.1    8.52                                        n-nonylphenyl                                                                           neo-undecyl    445.1    8.52                                        n-nonylphenyl                                                                           n-dodecyl      460.7    8.56                                        n-nonylphenyl                                                                           iso-dodecyl    460.7    8.50                                        n-nonylphenyl                                                                           neo-dodecyl    460.7    8.50                                        n-nonylphenyl                                                                           n-tridecyl     476.3    8.54                                        n-nonylphenyl                                                                           iso-tridecyl   476.3    8.48                                        n-nonylphenyl                                                                           neo-tridecyl   476.3    8.48                                        n-nonylphenyl                                                                           n-tetradecyl   491.8    8.51                                        n-nonylphenyl                                                                           iso-tetradecyl 491.8    8.46                                        n-nonylphenyl                                                                           neo-tetradecyl 491.8    8.46                                        n-nonylphenyl                                                                           n-pentadecyl   507.4    8.49                                        n-nonylphenyl                                                                           iso-pentadecyl 507.4    8.43                                        n-nonylphenyl                                                                           neo-pentadecyl 507.4    8.43                                        n-nonylphenyl                                                                           n-hexadecyl    522.9    8.45                                        n-nonylphenyl                                                                           iso-hexadecyl  522.9    8.41                                        n-nonylphenyl                                                                           neo-hexadecyl  522.9    8.41                                        n-nanylphenyl                                                                           n-heptadecyl   538.5    8.42                                        n-nonylphenyl                                                                           iso-heptadecyl 538.5    8.38                                        n-nonylphenyl                                                                           neo-heptadecyl 538.5    8.38                                        n-nonylphenyl                                                                           n-octyldecyl   554.0    8.38                                        n-nonylphenyl                                                                           iso-octyldecyl 554.0    8.34                                        n-nonylphenyl                                                                           neo-octyldecyl 554.0    8.34                                        n-nonylphenyl                                                                           n-nonadecyl    569.6    8.34                                        n-nonylphenyl                                                                           iso-nonadecyl  569.9    8.30                                        n-nonylphenyl                                                                           neo-nonyldecyl 569.6    8.30                                        n-nonylphenyl                                                                           n-eicosyl      585.1    8.30                                        n-nonylphenyl                                                                           iso-eicosyl    585.1    8.26                                        n-nonylphenyl                                                                           neo-eicosyl    585.1    8.26                                        n-nonylphenyl                                                                           linear and branched                                                 n-nonylphenyl                                                                           alkylaryl                                                           n-nonylphenyl                                                                           tolyl          358.1    8.43                                        n-nonylphenyl                                                                           ethylphenyl    373.7    8.45                                        n-nonylphenyl                                                                           cumyl          389.2    8.47                                        n-nonylphenyl                                                                           n-propylphenyl 389.2    8.37                                        n-nonylphenyl                                                                           n-butylphenyl  404.8    8.48                                        n-nonylphenyl                                                                           n-pentylphenyl 420.3    8.48                                        n-nonylphenyl                                                                           n-hexylphenyl  435.9    8.48                                        n-nonylphenyl                                                                           n-heptylphenyl 451.4    8.48                                        n-nonylphenyl                                                                           n-octylphenyl  467.0    8.47                                        n-nonylphenyl                                                                           n-nonylphenyl  482.6    8.46                                        n-nonylphenyl                                                                           n-decylphenyl  498.1    8.44                                        n-nonylphenyl                                                                           n-undecykphenyl                                                                              513.7    8.43                                        n-nonylphenyl                                                                           n-dodecylphenyl                                                                              529.2    8.40                                        n-nonylphenyl                                                                           n-tridecylphenyl                                                                             544.8    8.38                                        n-nonylphenyl                                                                           n-tetradecylphenyl                                                                           560.3    8.35                                        n-nonylphenyl                                                                           n-pentadecylphenyl                                                                           575.9    8.31                                        n-nonylphenyl                                                                           n-hexadecylphenyl                                                                            591.4    8.28                                        n-nonylphenyl                                                                           n-heptadecylphenyl                                                                           606.9    8.23                                        n-nonylphenyl                                                                           n-octadecylphenyl                                                                            622.5    8.18                                        n-nonylphenyl                                                                           n-nonadecylphenyl                                                                            638.1    8.13                                        n-nonylphenyl                                                                           n-eicosylphenyl                                                                              653.6    8.06                                        n-hexadecyl                                                                             methyl         330.0    8.77                                        n-hexadecyl                                                                             ethyl          345.5    8.74                                        n-hexadecyl                                                                             n-propyl       361.1    8.72                                        n-hexadecyl                                                                             n-butyl        376.6    8.70                                        n-hexadecyl                                                                             n-pentyl       392.2    8.68                                        n-hexadecyl                                                                             n-hexyl        407.7    8.66                                        n-hexadecyl                                                                             n-heptyl       423.3    8.64                                        n-hexadecyl                                                                             n-octyl        438.8    8.62                                        n-hexadecyl                                                                             n-nonyl        454.4    8.60                                        n-hexadecyl                                                                             n-decyl        470.0    8.57                                        n-hexadecyl                                                                             n-undecyl      485.5    8.55                                        n-hexadecyl                                                                             linear alkyl                                                        n-hexadecyl                                                                             n-dodecyl      501.0    8.52                                        n-hexadecyl                                                                             n-tridecyl     516.6    8.49                                        n-hexadecyl                                                                             n-tetradecyl   532.2    8.46                                        n-hexadecyl                                                                             n-pentadecyl   547.7    8.43                                        n-hexadecyl                                                                             n-hexadecyl    563.3    8.39                                        n-hexadecyl                                                                             n-heptadecyl   578.8    8.35                                        n-hexadecyl                                                                             n-octadecyl    594.4    8.30                                        n-hexadecyl                                                                             n-nonadecyl    609.9    8.25                                        n-hexadecyl                                                                             n-eicosyl      625.5    8.8                                         ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Calculated Molar Volumes and Solubility                                       Parameters for Selected Biphobes of the Form:                                  ##STR2##                                                                                                         Solubility                                                        Molar Volume,                                                                             Parameter                                 R.sub.1, R.sub.2                                                                           R          cc/mole     (cal/cc).sup.1/2                          ______________________________________                                        methyl       n-butyl    212.5       9.24                                      ethyl        n-butyl    243.6       9.12                                      n-propyl     n-butyl    274.7       9.03                                      n-butyl      n-butyl    305.8       8.94                                      n-pentyl     n-butyl    336.9       8.86                                      n-hexyl      n-butyl    368.0       8.79                                      n-heptyl     n-butyl    399.1       8.71                                      n-octyl      n-butyl    430.2       8.63                                      n-nonyl      n-butyl    461.3       8.54                                      n-decyl      n-butyl    492.4       8.43                                      n-undecyl    n-butyl    523.5       8.31                                      n-dodecyl    n-butyl    554.6       8.15                                      n-tridecyl   n-butyl    585.8       7.95                                      n-tetradecyl n-butyl    616.9       7.68                                      n-pentadecyl n-butyl    648.0       7.31                                      n-hexadecyl  n-butyl    679.1       6.77                                      n-heptadecyl n-butyl    710.2       5.93                                      n-octadecyl  n-butyl    741.3       4.47                                      tolyl                   349.5       8.47                                      ethylphenyl  n-butyl    380.6       8.50                                      n-propylphenyl                                                                             n-butyl    411.7       8.51                                      n-butylphenyl                                                                              n-butyl    442.8       8.49                                      n-pentylphenyl                                                                             n-butyl    473.9       8.45                                      n-hexylphenyl                                                                              n-butyl    505.0       8.40                                      n-heptylphenyl                                                                             n-butyl    536.1       8.32                                      n-octylphenyl                                                                              n-butyl    567.2       8.22                                      n-nonylphenyl                                                                              n-butyl    598.4       8.10                                      n-decylphenyl                                                                              n-butyl    629.5       7.93                                      n-undecylphenyl                                                                            n-butyl    660.6       7.72                                      n-dodecylphenyl                                                                            n-butyl    691.7       7.43                                      n-tridecylphenyl                                                                           n-butyl    722.8       7.04                                      n-tetradecylphenyl                                                                         n-butyl    753.9       6.48                                      n-pentadecylphenyl                                                                         n-butyl    785.0       5.64                                      n-hexadecylphenyl                                                                          n-butyl    816.1       4.20                                      methyl       Bisphenol A                                                                              334.0       8.12                                      ethyl        Bisphenol A                                                                              365.1       8.22                                      n-propyl     Bisphenol A                                                                              396.2       8.28                                      n-butyl      Bisphenol A                                                                              427.3       8.31                                      n-pentyl     Bisphenol A                                                                              458.4       8.31                                      n-hexyl      Disphenol A                                                                              489.5       8.29                                      n-heptyl     Bisphenol A                                                                              520.6       8.24                                      n-octyl      Bisphenol A                                                                              551.7       8.18                                      n-nonyl      Bisphenol A                                                                              582.8       8.09                                      n-decyl      Bisphenol A                                                                              614.0       7.97                                      n-undecyl    Bisphenol A                                                                              645.0       7.81                                      n-dodecyl    Bisphenol A                                                                              676.1       7.60                                      n-tridecyl   Bisphenol A                                                                              707.2       7.32                                      n-tetradecyl Bisphenol A                                                                              738.3       6.93                                      n-pentadecyl Bisphenol A                                                                              768.4       6.38                                      n-hexadecyl  Bisphenol A                                                                              800.5       5.53                                      n-heptadecyl Bisphenol A                                                                              831.6       4.08                                      tolyl        Bisphenol A                                                                              471.0       7.24                                      ethylphenyl  Bisphenol A                                                                              502.1       7.51                                      n-propylphenyl                                                                             Bisphenol A                                                                              533.2       7.68                                      n-butylphenyl                                                                              Bisphenol A                                                                              564.3       7.79                                      n-pentylphenyl                                                                             Bisphenol A                                                                              595.4       7.84                                      n-hexylphenyl                                                                              Bisphenol A                                                                              626.5       7.84                                      n-heptylphenyl                                                                             Bisphenol A                                                                              657.6       7.81                                      n-octylphenyl                                                                              Bisphenol A                                                                              688.7       7.74                                      n-nonylphenyl                                                                              Bisphenol A                                                                              719.8       7.62                                      n-decylphenyl                                                                              Bisphenol A                                                                              750.9       7.46                                      n-undecykphenyl                                                                            Bisphenol A                                                                              782.0       7.23                                      n-dodecylphenyl                                                                            Bisphenol A                                                                              813.1       6.91                                      n-tridecylphenyl                                                                           Bisphenol A                                                                              844.2       6.47                                      n-tetradecylphenyl                                                                         Bisphenol A                                                                              875.4       5.81                                      n-pentadecylphenyl                                                                         Bisphenol A                                                                              906.5       4.80                                      n-hexadecylphenyl                                                                          Bisphenol A                                                                              937.6       2.87                                      ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        Calculated Molar Volumes and Solubility                                       Parameters for Selected Multiphobes of the Form:                               ##STR3##                                                                                                          Solubility                                                          Molar Volume,                                                                           Parameter                                R.sub.1, R.sub.2, R'                                                                     k     Name      cc/mole   (cal/cc).sup.1/2                         ______________________________________                                        n-nonylphenyl                                                                            0     BiPhobe   482.6     8.46                                     n-nonylphenyl                                                                            1     TriPhobe  900.9     3.81                                     n-nonylphenyl                                                                            2     QuadPhobe 1319      >3.81                                    n-nonylphenyl                                                                            3     QuintPhobe                                                                              1737      --                                       n-nonylphenyl                                                                            4     HexPhobe  2156      --                                       n-nonylphenyl                                                                            5     HeptPhobe 2574      --                                       n-nonylphenyl                                                                            6     OctPhobe  2993      --                                       ______________________________________                                    

Molar volume contributions of less than about 70 cubic centimeters permole are generally undesirable in aqueous applications since dynamicdimer, trimer and tetramer water molecular aggregations (formed byhydrogen bonding of the water molecules) are generally prevalent in suchsolutions. As such, hydrophobes providing a molar volume contribution ofless than about 70 cubic centimeters per mole would not provide asignificant difference between the molar volume of the aggregated watermolecules and such smaller hydrophobes.

The foregoing and numerous other useful monohydroxyl and amino compoundsare well known as described in standard organic textbooks and otherreference works.

The complex hydrophobic groups, i.e., complex hydrophobes, useful inthis invention can be derived from compounds having at least one activehydrogen represented by the formula: ##STR4## wherein R₁ and R₂ are thesame or different and are hydrogen or a substituted or unsubstitutedmonovalent hydrocarbon residue, R₃ is a substituted or unsubstituteddivalent or trivalent hydrocarbon residue, each R₄ is the same ordifferent and is a substituted or unsubstituted divalent hydrocarbonresidue, each R₅ is the same or different and is a substituted orunsubstituted divalent hydrocarbon residue, R₆ is hydrogen, asubstituted or unsubstituted monovalent hydrocarbon residue or an ionicsubstituent, a and b are the same or different and are a value of 0 or1, and x and y are the same or different and are a value of 0 orgreater; provided at least two of R₁, R₂, R₃, R₄, R₅ and R₆ are ahydrocarbon residue having greater than 2 carbon atoms in the case ofR₁, R₂ and R₆ or having greater than 2 pendant carbon atoms in the caseof R₃, R₄ and R₅. The polymers of this invention are other than aterpolymer of styrene, maleic anhydride and a macromonomer derived frommaleic anhydride and a compound of formula (i) in which R₁ is hexadecyl,a is a value of 1, R₂ is tetradecyl, b is a value of 0, R₃ is ##STR5##R₄ is --CH₂ CH(tetradecyl)--, x is a value of 1, R₅ is --CH₂ CH₂ --, yis a value of 34 and R₆ is hydrogen.

Other complex hydrophobic groups, i.e., complex hydrophobes, useful inthis invention can be derived from compounds having at least one activehydrogen represented by the formula: ##STR6## wherein R₇ and R₈ are thesame or different and are hydrogen or a substituted or unsubstitutedmonovalent hydrocarbon residue, R₁₁ and R₁₄ are the same or differentand are hydrogen, a substituted or unsubstituted monovalent hydrocarbonresidue or an ionic substituent, R₉ and R₁₂ are the same or differentand are a substituted or unsubstituted divalent or trivalent hydrocarbonresidue, each R₁₀ is the same or different and is a substituted orunsubstituted divalent hydrocarbon residue, each R₁₃ is the same ordifferent and is a substituted or unsubstituted divalent hydrocarbonresidue, R₁₅ is a substituted or unsubstituted divalent hydrocarbonresidue, d and e are the same or different and are a value of 0 or 1,and f and g are the same or different and are a value of 0 or greater;provided at least two of R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ area hydrocarbon residue having greater than 2 carbon atoms in the case ofR₇, R₈, R₁₁ and R₁₄ or having greater than 2 pendant carbon atoms in thecase of R₉, R₁₀, R₁₂, R₁₃ and R₁₅.

Illustrative substituted and unsubstituted monovalent hydrocarbonresidues contain from 1 to about 50 carbon atoms or greater and areselected from alkyl radicals including linear or branched primary,secondary or tertiary alkyl radicals, such as methyl, ethyl, n-propyl,isopropyl, amyl, sec-amyl, t-amyl, 2-ethylhexyl and the like; arylradicals such as phenyl, naphthyl and the like; arylalkyl radicals suchas benzyl, phenylethyl, tri-phenylmethylethane and the like; alkylarylradicals such as octylphenyl, nonylphenyl, dodecylphenyl, tolyl, xylyland the like; and cycloalkyl radicals such as cyclopentyl, cyclohexyl,cyclohexylethyl and the like. The permissible hydrocarbon residues maycontain fluorine, silicon, or other non-carbon atoms.

Preferably, the substituted and unsubstituted hydrocarbon residues areselected from alkyl and aryl radicals which contain from about 1 to 30carbon atoms or greater. More preferably, the alkyl radicals containfrom 1 to 18 carbon atoms, while the aryl, arylalkyl, alkylaryl andcycloalkyl radicals preferably contain from 6 to 18 carbon atoms orgreater.

In a preferred embodiment of this invention, R₁, R₂, R₇ and R₈ canindividually be a hydrocarbon radical represented by the formula:##STR7## wherein R₁₆ and R₁₇ are as defined for R₁, R₂, R₇ and R₈ above,h and i are the same or different and are a value of 0 or 1, and R₁₈ isas defined for R₃ above. For compounds represented by formulae (i) and(ii), it is understood that each formula (iii) radical in a givencompound may be the same or different and the R₁₆ and/or R₁₇ groups maythemselves be a formula (iii) radical to provide complex hydrophobes ofa dendritic or of a cascading nature as described below. Further, R₄,R₅, R₁₀ and R₁₃ can individually be a hydrocarbon radical represented bythe formula:

    --CH[(OR.sub.19).sub.j OR.sub.20 ]--                       (iv)

wherein R₁₉ is as defined for R₄, R₅, R₁₀ and R₁₃ above, R₂₀ is asdefined for R₆, R₁₁ and R₁₄ above, and j is a value of 0 or greater.

Illustrative ionic substituents for R₆, R₁₁, R₁₄ and R₂₀ includecationic and anionic substituents such as sulfates, sulfonates,phosphates and the like. R₆, R₁₁, R₁₄ and R₂₀ may preferably be anorganic residue containing 1 or more hydroxyls or nitrogen derivativesor epoxides or other reactive groups which may or may not containunsaturation.

Other illustrative terminal groups which are described by R₆, R₁₁, R₁₄and R₂₀ include, for example, hydrocarbon residues which may containallylic or vinylic unsaturation, acrylic or methacrylic functionality,styryl or alpha-methylstyryl functionality, and the like, such as thereaction product between the terminal alcohol (R₆, R₁₁, R₁₄ and R₂₀ =H)and glycidyl methacrylate, isocyanatoethyl methacrylate, alpha,alpha-dimethyl-m-isopropenyl benzyl isocyanate (m-TMI), and the like.Other examples of terminal groups may include hydrocarbon residues ofalkyl, aryl, aralkyl, alkaryl, and cycloalkyl radicals which may or maynot be substituted with one or more of the following: hydroxyl,carboxyl, isocyanato, amino, mono- or disubstituted amino,.quaternaryammonium, sulfate, sulfonate, phosphate, epoxy, and the like and may ormay not contain other non-carbon atoms including silicon or fluorine.Also included can be divalent siloxy radicals. Other nonhydrocarbonterminal groups may include sulfates, phosphates, and the like.

Illustrative divalent hydrocarbon residues represented by R₃, R₄, R₅,R₉, R₁₀, R₁₂, R₁₃, R₁₅, R₁₈ and R₁₉ in the above formulae includesubstituted and unsubstituted radicals selected from alkylene,-alkylene-oxy-alkylene-, -arylene-oxy-arylene-, arylene, alicyclicradicals, phenylene, naphthylene, -phenylene-(CH₂)_(m) (Q)_(n) (CH₂)_(m)-phenylene- and -naphthylene-(CH₂)_(m) (Q)_(n) (CH₂)_(m) -naphthylene-radicals, wherein Q individually represents a substituted orunsubstituted divalent bridging group selected from --CR₂₁ R₂₂ --,--O--, --S--, --NR₂₃ --, --SiR₂₄ R₂₅ -- and --CO--, wherein R₂₁ and R₂₂individually represent a radical selected from hydrogen, alkyl of 1 to12 carbon atoms, phenyl, tolyl and anisyl; R₂₃, R₂₄ and R₂₅ individuallyrepresent a radical selected from hydrogen and methyl, and each m and nindividually have a value of 0 or 1. More specific illustrative divalentradicals represented by R₃, R₄, R₅, R₉, R₁₀, R₁₂, R₁₃, R₁₅, R₁₈ and R₁₉include, e.g., 1,1-methylene, 1,2-ethylene, 1,3-propylene, 1,6-hexylene,1,8-octylene, 1,12-dodecylene, 1,4-phenylene, 1,8-napthylene,1,1'-biphenyl-2,2'-diyl, 1,1'-binaphthyl-2,2'-diyl,2,2'-binaphthyl-1,1'-diyl and the like. The alkylene radicals maycontain from 2 to 12 carbon atoms or greater, while the arylene radicalsmay contain from 6 to 18 carbon atoms or greater. Preferably, R₃, R₄,R₅, R₉, R₁₀, R₁₂, R₁₃, R₁₅, R₁₈ and R₁₉ are an alkylene or aryleneradical. The permissible divalent hydrocarbon residues may containfluorine, silicon, or other non-carbon atoms.

Illustrative trivalent hydrocarbon residues represented by R₃, R₉, R₁₂and R₁₈ in the above formulae include substituted and unsubstitutedradicals selected from ##STR8## and the like, wherein R₂₆ is asubstituted or unsubstituted monovalent hydrocarbon residue as describedherein and R₂₇ is a substituted or unsubstituted divalent hydrocarbonresidue as described herein.

Of course, it is to be further understood that the hydrocarbon residuesin the above formulae may also be substituted with any permissiblesubstituent. Illustrative substituents include radicals containing from1 to 18 carbon atoms such as alkyl, aryl, aralkyl, alkaryl andcycloalkyl radicals; alkoxy radicals; silyl radicals such as --Si(R₂₈)₃and --Si(OR₂₈)₃, amino radicals such as --N(R₂₈)₂ ; acyl radicals suchas --C(O)R₂₈ ; acyloxy radicals such as --OC(O)R₂₈ ; carbonyloxyradicals such as --COOR₂₈ ; amido radicals such as --C(O)N(R₂₈)₂ and--N(R₂₈)COR₂₈ ; sulfonyl radicals such as --SO₂ R₂₈ ; sulfinyl radicalssuch as --SO(R₂₈)₂ ; thionyl radicals such as --SR₂₈ ; phosphonylradicals such as --P(O)(R₂₈)₂ ; as well as halogen, nitro, cyano,trifluoromethyl and hydroxy radicals and the like, wherein each R₂₈ canbe a monovalent hydrocarbon radical such as alkyl, aryl, alkaryl,aralkyl and cycloalkyl radicals, with the provisos that in aminosubstituents such as --N(R₂₈)₂, each R₂₈ taken together can alsocompromise a divalent bridging group that forms a heterocyclic radicalwith the nitrogen atom, in amido substituents such as --C(O)N(R₂₈)₂ and--N(R₂₈)COR₂₈, each R₂₈ bonded to N can also be hydrogen, and inphosphonyl substituents such as --P(O)(R₂₈)₂, one R₂₈ can by hydrogen.It is to be understood that each R₂₈ group in a particular substituentmay be the same or different. Such hydrocarbon substituent radicalscould possibly in turn be substituted with a permissible substituentsuch as already herein outlined above.

Preferred alkylene oxides which can provide random or block oxyalkyleneunits in the complex hydrophobe compounds represented by formulae (i)and (ii) include alkylene oxides such as ethylene oxide, propyleneoxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2- and 2,3-pentyleneoxide, cyclohexylene oxide, 1,2-hexylene oxide, 1,2-octylene oxide,1,2-decylene oxide, and higher alpha-olefin epoxides; epoxidized fattyalcohols such as epoxidized soybean fatty alcohols and epoxidizedlinseed fatty alcohols; aromatic epoxides such as styrene oxide and2-methylstyrene oxide; and hydroxy- and halogen-substituted alkyleneoxides such as glycidol, epichlorohydrin and epibromohydrin. Thepreferred alkylene oxides are ethylene oxide and propylene oxide. Alsoincluded can be hydrocarbon residues from substituted and unsubstitutedcyclic esters or ethers such as oxetane and tetrahydrofuran. It isunderstood that the compounds represented by formulae (i) and (ii)herein can contain random and/or block oxyalkylene units as well asmixtures of oxyalkylene units. It is further understood that each R₄,R₅, R₁₀, R₁₃ and R₁₉ group in a particular substituent for all positivevalues of x, y, f, g and j respectively can be the same or different.

The values of x, y, f, g and j are not narrowly critical and can varyover a wide range. For example, the values of x, y, f, g and j can rangefrom 0 to about 200 or greater, preferably from about 0 to about 100 orgreater, and more preferably from about 0 to about 50 or greater. Anydesired amount of alkylene oxide can be employed, for example, from 0 toabout 90 weight percent or greater based on the weight of the complexhydrophobe compound.

Referring to the general formulae (i) and (ii) above, it is appreciatedthat when R₁, R₂, R₇ and/or R₈ are a hydrocarbon residue of formulae(iii) above, the resulting compound may include any permissible numberand combination of hydrophobic groups of the dendritic or cascadingtype. Such compounds included in the above general formulae should beeasily ascertainable by one skilled in the art. Illustrative complexhydrophobes useful in this invention and processes for preparationthereof are disclosed in copending U.S. patent application Ser. No.(07/887,648), incorporated herein by reference.

In a preferred embodiment of this invention, the structure shown informula (iii) can be a residue of the reaction product betweenepichlorohydrin and an alcohol, including those alcohols whose residuescan be described by formula (iii), or a phenolic, or a mixture thereof.The structures which result can be described as complex hydrophobes of adendritic or of a cascading nature. Pictorially, they can be describedas shown below: ##STR9##

Other complex hydrophobic groups, i.e., complex hydrophobes, useful inthis invention can be derived from macromonomer compounds disclosed incopending U.S. patent application Ser. No. 07/887,645 and copending U.S.patent application Ser. No. 07/887,646, both of which are incorporatedherein by reference.

The polymers of this invention may be structurally defined to includethose compounds having the formula:

    A[B(C).sub.y',].sub.x'                                     (II)

wherein A is a water-soluble polymer segment; B is a connecting segmentcomprising a covalent bond or a polyvalent organic radical; C is ahydrophobic or complex hydrophobic group; the number of hydrophobe andcomplex hydrophobe segments, x', defined by B(C)_(y'), is greater than0; the number of hydrophobes and complex hydrophobes, C, for eachhydrophobic segment, defined as y', is greater than or equal to 1, y'can have values of greater than 1, i.e., ##EQU2## such that the polymercan have an amount of bunching comprising at least two hydrophobicgroups per hydrophobic segment. The polymer has an amount of complexhydrophobic groups sufficient to provide for enhanced thickening ofaqueous solutions containing the polymer. The y' value in Equation IIsets forth the number of hydrophobic or complex hydrophobic groups perhydrophobic segment. The x' value sets forth the average number ofhydrophobic segments per molecule. Equation III sets forth the amount ofbunching in that the average number of hydrophobic and complexhydrophobic groups per hydrophobic segment, y', can be greater than 1.The average number of hydrophobic and complex hydrophobic groups perhydrophobic segment, y', is defined as a total number of hydrophobic andcomplex hydrophobic groups (i.e., the summation of all hydrophobic andcomplex hydrophobic groups per hydrophobic segment, y'x'), divided bythe total number of hydrophobic segments, _(x').

The connecting segment, B, may be water-soluble or water-insoluble. Thehydrophobic segments, B(C)_(y'), may be attached in a pendant fashion tox' terminal and/or interior bonds of the water-soluble polymer backboneA; or the connecting segment, B, may be incorporated as part of thepolymer backbone between a plurality of water-soluble polymer segments.

The polymers of this invention may have utility in both aqueous andnon-aqueous systems. They may be utilized to treat inorganic particulatematerials used as fillers and pigments to alter their surfacecharacteristics, thereby enhancing particle wetting when incorporated ina resin system. For example, fillers like silica, zinc oxide,wollastonite, calcium carbonate, glass fibers, clays, molecular sieves,and the like can be suspended more effectively into resin compositionscontaining a relatively small amount of the polymers of this invention.The polymers of this invention can also be used to treat the surface ofthese particulate materials before they are supplied or incorporated ina resin composition. If the particulate material which is supplied tothe resin has a water-rich layer on its surface, or is hydrated, then itis expected that the water-soluble portion of the polymer of thisinvention will to some extent dissolve in that layer and thereby provideat least a monolayer of the polymer structure about the particulatematerial. Consequently, the hydrophobic and complex hydrophobic groupsof the polymer will extend away from the water-rich portion of thesurface of the particles and will be incorporated into the resincontinuous phase (matrix) of the resin composition to which theseparticulate materials are added. The advantage in that particularinstance is that by wetting the surface with a material which iscompatible with that surface, and by providing it with hydrophobic andcomplex hydrophobic groups which are readily compatible with the resinto which the particulate material is being incorporated, one is betterable to wet the particulate material with the resin to which it is beingadded, thereby suspending the particulate material in the resin moreeffectively.

When used in an aqueous solution, the water-soluble organic polymers ofthis invention are provided in an effective amount to produce thickeningof the aqueous solution. An "effective thickening amount" is defined asthe quantity of polymer, whether alone or in combination with polymerthickeners of the prior art, required to produce enhanced thickening.Such amount will usually range between about 0.05 to about 10 weightpercent, preferably between about 0.1 to about 5 weight percent, andmost preferably between about 0.2 to about 2 weight percent of the totalcomposition. Such thickened compositions are useful in a wide variety ofapplications, such as latex compositions.

The polymers of this invention are derived from reactions involvingwater-soluble monomeric or polymeric reactants and hydrophobic andcomplex hydrophobic reactants, i.e., compounds containing hydrophobicand/or complex hydrophobic groups. Optionally, a connecting monomer mayalso be provided as a linking compound between the water-solublereactant and the hydrophobic or complex hydrophobic reactant.

The polymers of the present invention may be made by:

(A) bonding the requisite hydrophobes and complex hydrophobes to awater-soluble polymer reactant containing functional groups availablefor linking the hydrophobes and complex hydrophobes to the polymerwithout extending the chain length of the water-soluble portions of thepolymer;

(B) reacting condensation monomers and/or prepolymers to formcondensation polymers wherein at least one of which contains therequisite complex hydrophobe component; or

(C) reacting olefinically unsaturated monomers and/or prepolymers byaddition polymerization, wherein at least one of which contains therequisite complex hydrophobe component.

The polymer designated (A) above can be any water-soluble, naturallyoccurring polymer, any water-soluble, modified naturally occurringpolymer, or any water-soluble, synthetically produced polymer, such asderived from the prepolymers hereinafter described for (B) and (C).

Illustrative of such naturally occurring polymers are: gelatin, naturalgums, casein, starch, alginates, and the like. Modified naturallyoccurring polymers are the modified cellulosic polymers wherein themodification causes the cellulosic polymer to be water-soluble.Illustrative of such polymers are starch derivatives; the hydroxyethylcellulosics formed by reacting ethylene oxide with cellulose to a degreesufficient to form a polymer soluble in some proportion in water;water-soluble carboxymethyl cellulose; quarternerized ammoniumsubstituted cellulosics such described in U.S. Pat. No. 3,472,840, andother such cellulosic derivations. The other naturally occurringpolymers may all be oxyethylated by reaction with ethylene oxide, orreacted with other reactants which provide functionality and do notappreciably hinder the intrinsic solubility of the polymers in water.

With respect to the condensation polymers designated (B) above,illustrative examples include condensation polyamides and polyesters,polyethers, and the like. In this latter regard, the term condensationpolymer is defined to encompass not only those polymers formed frommonomer molecules which combine with the loss of simple molecules, suchas water, but also to include polymers formed by chemical reactions inwhich the rearrangement of the functional moieties of the monomermolecules during polymerization avoids a loss of a simple molecule.

These polymers are achieved by known condensation reactions by reactingpolyfunctional reactants which possess sufficient complementaryfunctional groups to allow condensation and polymerization. Examples ofsuch functional groups which are considered complementary for effectingcondensation and polymerization are the following:

    ______________________________________                                        Functional    Complementary Functional                                        Group         Group                                                           ______________________________________                                                      COOH                                                            NH.sub.2      COX*                                                                          (*X is halogen)                                                 OH SH                                                                                        ##STR10##                                                                    ClCl (Williamson synthesis)                                                   COOR*                                                                         (*OR is an ester forming group)                                                ##STR11##                                                                    CHO                                                                           (aldehyde)                                                                    CRO                                                                           (ketone)                                                                      CH.sub.2 OH                                                                   (Methylol)                                                                    CONH.sub.2                                                                     ##STR12##                                                      ______________________________________                                    

Obviously, functional group combinations other than those cited abovecan be appropriately used in the practice of this invention.

The polymers designated (C) above are the product of the reaction ofmonomeric or prepolymer components interreacting by additionpolymerization through olefinically unsaturated double bonds. Withrespect to the addition polymers, illustrative examples includepolyacrylics; such as polyacrylates, polymethacrylates,polyhydroxyethylacrylates and polyacrylamides; polyvinyl compounds; andthe like.

The present invention relates to a process for producing a water-solubleorganic polymer which comprises:

(a) bonding (1) a functional group-containing hydrophobic reactant thathas at least one complex hydrophobic group and that can have ahydrophobe bunch of at least two hydrophobic groups, complex hydrophobicgroups or mixtures with (2) a water-soluble polymer reactant containinga complementary functional group whereby said hydrophobic reactant iscovalently bonded to the polymer; or

(b) interreacting (1) a functional group-containing hydrophobic reactantthat has at least one complex hydrophobic group and that can have ahydrophobe bunch of at least two hydrophobic groups, complex hydrophobicgroups or mixtures with (2) a complementary functional water-solubleprepolymer or monomer whereby the two are copolymerized to provide awater-soluble polymer containing said hydrophobic reactant; or

(c) interreacting (1) a functional group-containing hydrophobic reactantthat has at least one complex hydrophobic and optionally hydrophobicgroup with (2) a complementary functional water-soluble prepolymerwhereby the two are copolymerized to provide a water-soluble polymerhaving at least one complex hydrophobic group and at least onehydrophobe bunch containing at least two hydrophobic groups, complexhydrophobic groups or mixtures.

In the broadest sense, the water-soluble organic polymers of thisinvention may be prepared using either of two basic procedures. In afirst embodiment for making condensation polymers (B) or additionpolymers (C) as described above, the hydrophobic and complex hydrophobicreactants and water-soluble polymeric or monomeric reactants, andoptionally connecting monomers, are reacted either prior to or duringthe polymerization to form the polymer of this invention having complexhydrophobic groups. In a second embodiment for making any of thepolymers (A), (B), or (C) above, the water-soluble polymer reactant is arelatively high-molecular weight polymer, having a weight averagemolecular weight of about 10,000 or greater. In this embodiment, thewater-soluble polymer reactant has a plurality of functional side and/orterminal groups which are reactive with functional groups of hydrophobicand complex hydrophobic compounds which allow bonding onto thewater-soluble organic polymer to provide an amount of hydrophobic andcomplex hydrophobic groups sufficient to provide for enhanced thickeningof aqueous solutions containing the polymer.

In the first embodiment, a variety of polymerization processes can beutilized in order to produce polymers having hydrophobic and complexhydrophobic groups and optionally bunched hydrophobe segments. One suchprocess which is quite effective, is to perform a compound having abunch of hydrophobic and complex hydrophobic groups prior topolymerization. In this way, the incorporation of bunched hydrophobesegments is insured. Using such a process, the preforming of thehydrophobe and complex hydrophobe reactant can be achieved by reactinghydrophobic and complex hydrophobic reactants together or with aconnecting monomer to produce a hydrophobic or complex hydrophobicreactant having bunched hydrophobe segments. These hydrophobic andcomplex hydrophobic reactants can then be polymerized with awater-soluble polymeric or monomeric reactant to provide a water-solubleorganic polymer.

A second polymerization process relies upon the kinetics of thepolymerization reaction to provide formation of bunched hydrophobesegments. By providing a difunctional, connecting monomer havingfunctional moieties which selectively polymerize with the functionalmoieties of the hydrophobic and complex hydrophobic reactant, even inthe presence of the water-soluble polymer reactant (having functionalmoieties less reactive with the connecting monomer), bunched hydrophobesegments can be formed initially, followed by extension of the polymerwith the water-soluble polymer reactant.

A third polymerization process involves making a prepolymer of thewater-soluble polymer segment and joining such prepolymers with anequivalent or larger molar amount of hydrophobic and complex hydrophobiccompounds having single hydrophobic groups. Using such a process, theformation of bunched hydrophobe segments is insured on the basis ofstatistical considerations. As the molar ratio of hydrophobic andcomplex hydrophobic reactants to prepolymer is increased, the number ofhydrophobes per bunch is correspondingly increased.

Conceivably, variations of these procedures for achieving hydrophobebunch formation, although much less effective, may be to (1) graft alarge molar amount of hydrophobic or complex hydrophobic reactant havinga single hydrophobe in a random fashion to a preformed, water-solublebackbone or alternatively (2) copolymerize an excessive molar amount ofhydrophobic or complex hydrophobic reactant having a single hydrophobewith low-molecular weight water-soluble monomers. If enough hydrophobicand complex hydrophobic reactant is added, bunching might result. Adrawback to these procedures is that the amount of hydrophobic andcomplex hydrophobic reactants required to achieve a substantial degreeof bunching may limit the water-solubility of the polymer and itsability to form intermolecular hydrophobic associations.

The polymers of this invention contain hydrophobes and complexhydrophobes derived from hydrophobic reactants which may be reacteddirectly, or through a connecting monomer, with the water-solublepolymer reactants or may be bonded onto a water-soluble backbone or aside group attached to the backbone. The hydrophobic and complexhydrophobic reactants contain at least one hydrophobic group, or in apreferred embodiment, comprise a plurality of hydrophobic groups. Thehydrophobe and complex hydrophobe compounds may be monofunctional ordifunctional depending upon the reactive process required to chemicallybond the hydrophobic reactants to the water-soluble reactant or to theconnecting monomer.

Some of the specific examples of preferred hydrophobic and complexhydrophobic reactants which can be used to form bunches of hydrophobesthat can be incorporated into the polymer either pendantly or integrallyunder the appropriate reaction conditions or sequence of reactions arecomplex alkylaryl reactants. Most preferred hydrophobic reactantsinclude complex alkylaryls having at least about 8 carbon atoms.Preferred complex hydrophic compounds include complex polyalkylaryls.Particularly preferred hydrophobic compounds include bis-nonylphenol,bis-octylphenol and the reaction product of nonylphenol and nonylphenolglycidyl ether.

The amount of hydrophobic compound which can be added to produce thehydrophobes and complex hydrophobes on the water-soluble polymers mayrange from about 0.01 to about 10 weight %, more preferably about 0.1 toabout 5 weight %, and most preferably from about 0.5 to about 2.5 weight% of the total polymer product.

With respect to the polymer reactants designated (A), the complexhydrophobic compounds may be coupled to such polymer reactants through afunctional group along the polymer. The functional groups of thewater-soluble polymer reactants contain moieties which provide thereactivity required to chemically bond the water-soluble polymerreactant to the hydrophobic reactants. Such moieties can be eitheractive hydrogen, e.g. hydroxyl, sulfhydryl, amino and the like or thecorresponding complementary the like. In the case where the reactants ofthe water-soluble polymer reactants and the hydrophobe and complexhydrophobe reactant are identical, a connecting monomer of thecorresponding complementary type may be used to bind the hydrophobe andcomplex hydrophobe to the water-soluble polymer.

Other examples of such functional groups include, but at not limited to:hydroxyls; sulfhydryls, aminos, ethylenic unsaturations, epoxides,carboxylic acids, carboxylic esters, carboxylic acid halides, amides,phosphates, sulfonates, sulfonyl halides, organic silanes, acetylenes,phenols, cyclic carbonates, and carbodiimides. The coupling of suchhydrophobic compounds to the polymer through such active hydrogens canbe achieved by reactions in which such active hydrogens participate,such as the functional condensation groups depicted above.

For example, hydroxyethylcellulose, polyvinyl alcohol orpolyacrylamides, can have bunched hydrophobe substitution introducedtherein by reacting functional hydroxyethyl, hydroxyl or amino groups,respectively on these polymer with a complementary functional complexhydrophobic compound. Obviously, many other kinds of complementaryfunctional compounds containing bunched hydrophobes within thecontemplation of this invention will be apparent to those skilled in theart.

With respect to the polymer reactants designated (B), the hydrophobe orcomplex hydrophobe containing reactant is typically polyfunctional,preferably difunctional, so as to assure the formation of a polymer.Many kinds of complementary difunctional compounds containing complexhydrophobes and optionally bunched hydrophobes within the contemplationof this invention will be apparent to those skilled in the art.

In a preferred embodiment, a connecting monomer is also provided as alinking compound between the water-soluble polymer reactant and ahydrophobe or complex hydrophobe reactant. The connecting monomer ispreferably difunctional, having at least two terminal functional groupswhich provide the reactivity required to chemically bond to thehydrophobic reactants to the water-soluble polymer reactant.

The amount of connecting monomers which can be reacted to awater-soluble reactant or hydrophobic reactants may range from about 0.1to about 10 weight %, more preferably from about 0.5 to about 7 weight%, most preferably 1.5 to about 4 weight % of the total polymer product.

The complex hydrophobic reactant's functionality will be complementaryto those of other reactants, as set forth above, to produce the desiredwater-soluble polymer. In making such polymers water-soluble, thecomplementary reactants should contain polar groups which are notfunctional groups participating in the condensation reaction to providesufficient water-solubility in the polymer. When the polymer is formed,the polymer will either possess the desired water-solubility or can berendered water-soluble by ionization or by grafting polar groups such asmethylol or hydroxyethyl groups to active hydrogen containing moietiesexisting along the polymer chain. In the preferred case, at least one ofthe complementary reactants, i.e., the water-soluble polymer reactant,used to form the polymer contains sufficient repeating oxyethylenegroups or aminoethyl groups to render the resulting polymerwater-soluble, even though the polymer contains the bunched hydrophobecontent of this invention.

An illustrative portion of the condensation polymer designated (B) is:

    [--X--Y--Z--]                                              (VI)

wherein

(1) X is a divalent radical derived from a water-soluble polymerreactant having the following structure: e-R² -e, in which e is one ofthe functional groups listed above and R² is a divalent hydrocarbonradical such as: ##STR13## in which x" is an integer large enough tocause the resulting polymer to possess water-solubility and y" is aninteger less than x";

(2) Y is a divalent radical derived from a connecting monomer having thefollowing structure: f-R³ -f, in which f is one of the functional groupslisted above as being complementary functional, and R³ is any divalenthydrocarbon radical which with the composition of R² and Z provides forthe desired water-solubility; and

(3) Z is a divalent hydrocarbon radical derived from a hydrophobic orcomplex hydrophobic reactant having the following choice of structures:e-R⁴ -e and/or f-R⁴ -f, in which R⁴ contains at least one hydrophobe orcomplex hydrophobe containing moiety; e and f are as defined above, andthe selection of each is predicted upon the stoichiometric ratio of e tof in order to achieve the desired molecular weight of the polymer and toinsure the incorporation of bunched hydrophobes of Z into the polymericstructure. When R⁴ contains only one hydrophobic or complex hydrophobicgroup, the selective reactivity between Y and Z and the size of Y can besufficient to provide for bunching of hydrophobes in Z. In other words Ycan be sufficiently small and can separate at least two hydrophobic orcomplex hydrophobic groups in the Z radicals to provide the hydrophobicand complex hydrophobic groups in sufficient proximity of closeassociation to produce hydrophobic associations resulting in enhancedthickening of aqueous solutions containing such polymers.

With respect to the polymers designated (C), polymeric formation followsthe rules of polymers (B) above, i.e., the reactants are selected toyield a polymer which is water-soluble and which contains the requisitecomplex hydrophobes and optionally bunched hydrophobes. Thepolymerization of the olefininically unsaturated monomers which make uppolymer (C) may be achieved by any of the known addition polymerizationssuch as free-radical, anionic, cationic, or metal coordination methods.The polymerization may be effected interfacially, in solution, emulsion,suspension, and the like. In the typical case of polymerization willutilize at least two (2) copolymerizable components, one of whichprovides the water-solubility to the polymer (either as a result ofcopolymerization or as a result of treatment after copolymerization),and the other of which provides the desired bunched hydrophobe contentin the polymer.

Illustrative of such water-solubilizing components are the following:##STR14## wherein R⁵ is CH₃ -- or H--. The third example of vinylacetatewould require hydrolysis of the acetyl group to produce sufficient vinylalcohol moieties to be water-soluble.

Other water solubilizing components are known to those skilled in thechemical arts. Illustrative olefinically unsaturated monomericcomponents which can be included in making the polymer (C) structure,include vinyl acetate (not later hydrolyzed), vinyl propionate, vinylbutyrate, styrene, alpha-methyl styrene, maleic anhydride, fumaric acid,methyl fumarate, p-chloro-styrene, methyl acrylate, methyl methacrylate,1-hydroxy propyl acrylate, 2-hydroxyethyl acrylate, and the like.

Relative molar amounts of water-soluble polymer reactants, hydrophobicand complex hydrophobic reactants and connecting monomers may verydepending upon the reaction process used. Bonding of complex hydrophobicreactants into polyfunctional water-soluble polymer reactants having aplurality of functional side groups can be conducted with an amountsufficient to produce polymers having complex hydrophobic groupsproviding for enhanced thickening of aqueous solutions containing suchpolymers.

The temperature during the polymerization reaction may vary dependingupon the particular type of polymers being produced. For the preferredpolyethers, a convenient range is from about 40° C. to about 120° C.,preferably from about 60° C. to about 110° C. The reaction temperatureshould be selected to obtain a reasonably fast reaction rate whileavoiding undesirable side reactions. The water-soluble organic polymerproduct may be isolated from the reaction medium by procedures wellestablished in the art, including evaporation, distillation,precipitation, filtration and other isolation procedures.

Suitable adjuvants may be provided during the formation ofwater-soluble, thermoplastic, organic polymers of this inventionincluding solvents and catalysts well known to those skilled in the art.

In general catalysts are chosen which enhance the type of chemistryemployed to product the polymers of this invention.

The free radical addition polymerization method can be accomplished byeither thermally generated free radicals or by use of a redox system.Frequently employed free radical catalysts include persulfates,perphoshates, perborates, hydrogen peroxide, organic acyl peroxides,organic diacyl peroxides, organic hydroperoxides and organic azocompounds, and the like. In redox systems the reductants may besulfites, sodium formaldehyde sulfoxylate, ascorbic acid, and the like;trace amounts of polyvalent metal ions, such as Fe++ ion, can be used tofurther activate the catalyst in these systems. In addition chaintransfer agents such as mercaptans may be used to regulate the molecularweight and molecular weight distribution of the final polymer.

In the condensation polymerization method catalysts are again chosenbased on the type of chemistry being employed. Thus, for polyesters madeby direct esterification the well known acid or base catalysts maysuffice, while for transesterification metal alkoxides or organic metalsalts such as alkyl titanates, aluminates, stannates, plumbates, and thelike may be used.

An enhancement of thickening (herein termed "co-thickening") can resultupon the addition of a surfactant to an aqueous system containing thepolymer of this invention. In some cases the thickening can be enhancedup to about 40 times the viscosity afforded by the polymer alone. A widerange of surfactants may be used in an amount of about 0.1 to 0.5 partssurfactant per part polymer, same basis.

On the basis of an aqueous system containing about 0.1 to 5% by weightof polymer solids, a useful amount of surfactant for optimumco-thickening is about 0.1 to 1.0% by weight of the total system. Asindicated, the amounts of polymer and surfactant cothickener may verywidely, even outside these ranges, depending on polymer and surfactanttype and other components of the aqueous system to be thickened.However, the co-thickening can reach a maximum as surfactant is addedand then decreased. Hence, it may be uneconomical to employ surfactantin amounts outside the stated concentrations and polymer/surfactantratios, but this can be determined in a routine manner in each case.

The surfactants which may be used include nonionics and anionics, singlyor in combination, the selection necessarily depending uponcompatibility with other ingredients of the thickened or thickenabledispersions of this invention. Cationic and amphoteric surfactants mayalso be used provided they are compatible with the copolymer and otheringredients of the aqueous system, or are used in such small amounts asnot to cause incompatibility.

Suitable anionic surfactants that may be used include the higher fattyalcohol sulfates such as the sodium or potassium salt of the sulfates ofalcohols having from 8 to 18 carbon atoms, alkali metal salts or aminesalts of high fatty acid having 8 to 18 carbon atoms, and sulfonatedalkyl aryl compounds such as sodium dodecyl benzene sulfonate. Examplesof nonionic surfactants include alkylphenoxypolyethoxyethanols havingalkyl groups of about 7 to 18 carbon atoms and about 9 to 40 or moreoxyethylene units such as octylphenoxypolyethoxyethanols,dodecylphenoxypolyethoxyethanols; ethylene oxide derivatives oflong-chain carboxylic acids, such as lauric, myristic, palmitic, oleic;ethylene oxide condensates of long-chain alcohols such as lauryl orcetyl alcohol, and the like.

Examples of cationic surfactants include lauryl pyridinium chloride,octylbenzyltrimethylammonium chloride, dodecyltrimethylammonium chloridecondensates of primary fatty amines and ethylene oxide, and the like.

The foregoing and numerous other useful nonionic, anionic, cationic, andamphoteric surfactants are described in the literature, such asMcCutcheon's Detergents & Emulsifiers 1981 Annual, North AmericaEdition, MC Publishing Company, Glen Rock, N.J. 07452, U.S.A.,incorporated herein by reference.

In general, solvents and non-solvents (or mixtures of solvents,non-solvents, other organics and volatiles) can be used to manipulatethe viscosity of polymer containing systems. In the examples herein, itis interesting to note how mineral spirits act like co-thickener, andhow the water solubility of the other solvent influences how muchmineral spirits can be added before the solution separates into a twophase system. The co-thickening with mineral spirits has utility intextile printing pastes, and in waterborne automotive basecoats. Thesesystems usually contain mineral spirits (because of the pigments usedtherein), so that the mineral spirits provide a economical way ofincreasing viscosity and improving the efficiency of the thickener.

As used herein, the term "complex hydrophobe" is contemplated to includeall permissible hydrocarbon compounds having 2 or more hydrophobegroups, e.g., bis-dodecylphenyl, bis-nonylphenyl, bis-octylphenyl andthe like.

For purposes of this invention, the term "hydrocarbon" is contemplatedto include all permissible compounds having at least one hydrogen andone carbon atom. In a broad aspect, the permissible hydrocarbons includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic organic compounds which can besubstituted or unsubstituted.

As used herein, the term "substituted" is contemplated to include allpermissible substituents of organic compounds unless otherwiseindicated. In a broad aspect, the permissible substituents includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic substituents of organiccompounds. Illustrative substituents include, for example, alkyl,alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl,halogen and the like in which the number of carbons can range from 1 toabout 20 or more, preferably from 1 to about 12. The permissiblesubstituents can be one or more and the same or different forappropriate organic compounds. This invention is not intended to belimited in any manner by the permissible substituents of organiccompounds.

The invention is illustrated by certain of the following examples.

EXAMPLE 1 Preparation of 1,3-Bis(nonylphenoxy)-2-propanol

To a five neck, two liter round bottom flask equipped with an additionfunnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and adecanting head with a water-cooled condenser were added 220 grams (1.00mole) of nonylphenol and 250 milliliters of cyclohexane. The solutionwas then heated to reflux and 2.8 grams (1.3 wt. % based on nonylphenol)of potassium hydroxide in 10 milliliters of water was slowly added tothe flask. After essentially all the water was recovered in thedecanting head (10 milliliters+1 milliliter formed), 250.7 grams (0.91mole) of nonylphenyl glycidyl ether as added dropwise. During theaddition of the glycidyl ether, the reaction temperature was maintainedbetween 60° and 80° C. After the addition was complete, the solution wasrefluxed for four hours. The contents of the flask were then washed witha five percent aqueous solution of phosphoric acid, and the organiclayer was separated from the water layer and washed twice with deionizedwater. The reaction mixture was then placed in a one liter round bottomflask, and the remaining cyclohexane and unreacted nonylphenol wererecovered by distillation, first at atmospheric pressure, then undervacuum at 0.2 mm Hg. The kettle temperature was not allowed to exceed180° C. during the distillation to prevent discoloration of the product.The concentrated solution was then refiltered to give 425 grams of apale-yellow liquid. End-group MW analysis gave a molecular weight of506.8 (theoretical MW=496.8). Ir and nmr spectra were identical topreviously recorded spectra for the compound.

EXAMPLE 2 Preparation of 1,3-Bis(nonylphenoxy)-2-propanol

To a five neck, two liter round bottom flask, equipped with an additionfunnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and adecanting head with a water-cooled condenser, were added 300 millilitersof cyclohexane and 451.7 grams (2.05 mole) of nonylphenol. The solutionwas then heated to reflux and 58.9 grams (1.05 mole) of potassiumhydroxide in 60 milliliters of water was slowly added via the additionfunnel. After essentially all the water was recovered in the decantinghead (60 milliliter+19 milliliters formed), the reaction was cooled to40° C., and 92.5 grams (1.00 mole) of epichlorohydrin was slowly added.During the addition, the reaction temperature was maintained below 60°C. by controlling the rate of epichlorohydrin addition. After all theepichlorohydrin was added, the solution was allowed to stir for onehour, and then brought to reflux for an additional three hours. Thereaction mixture was then filtered under vacuum through a steam-jacketedBuchner funnel to remove the potassium chloride formed as a by-product.The filtration process was performed a total of three times to removethe majority of the salts. The reaction mixture was then placed in a oneliter round bottom flask, and the remaining cyclohexane and unreactednonylphenol were recovered by distillation, first at atmosphericpressure, then under vacuum at 0.2 mm Hg. The kettle temperature was notallowed to exceed 180° C. during the distillation to preventdiscoloration of the product. The concentrated solution was thenrefiltered to give 275 grams of a pale-yellow liquid. End-group MWanalysis gave a molecular weight of 459.7 (theoretical MW=496.8). Ir andnmr spectra were identical to previously recorded spectra for thecompound.

EXAMPLE 3 Preparation of 5 Mole Ethoxylate of1,3-Bis(nonylphenoxy)-2-propanol

To a 500 milliliter, stainless steel, high pressure autoclave wascharged 200 grams (0.40 mole) of 1,3-bis(nonylphenoxy)-2-propanol, whichcontained a catalytic amount of the potassium salt of the alcohol asdescribed in Example 1. After purging the reactor with nitrogen, thealcohol was heated to 130° C. with stirring, and 86.9 grams (2.0 mole)of ethylene oxide was added over a two hour period. The reactiontemperature and pressure were maintained from 130° C. to 140° C. and 60psig during the course of the reaction. After the addition of ethyleneoxide was complete, the reaction mixture was held at 140° C. for anadditional hour to allow all the ethylene oxide to cook out. Thereaction mixture was dumped while hot, under nitrogen, and neutralizedwith acetic acid to yield 285 grams of a pale-yellow liquid.

EXAMPLE 4 Preparation of Adduct of Nonylphenyl Glycidyl Ether and 5 MoleEthoxylate of 1,3Bis(nonylphenoxy)-2-propanol

To a five neck, one liter, round bottom flask equipped as in Example 1was added 119.8 grams (0.17 mole) of the 5 mole ethoxylate of1,3-bis(nonylphenoxy)-2-propanol and 100 milliliters of cyclohexane. Themixture was refluxed (100° C.) for one hour to remove residual water,and then cooled to 50° C. under nitrogen to add 0.5 grams of BF₃ /Et₂ O.Nonylphenyl glycidyl ether (46.0 grams, 0.17 mole) was then added to theflask over a one hour period, and the reaction was heated to reflux.After three hours at reflux, the reaction mixture was transferred to aseparatory funnel, while hot, and washed with a saturated aqueoussolution of sodium bicarbonate. The organic layer was separated from thewater layer, and washed twice with hot deionized water. The washes wereperformed at 50° C. to facilitate the separation of the two layers. Thewater and cyclohexane were then evaporated from the organic layer, undervacuum, to yield 145 grams of a pale-yellow, viscous liquid. End-groupmolecular weight analysis gave a molecular weight of 880 (theoreticalmolecular weight=993).

EXAMPLE 5 Preparation of Poly(nonylphenol glycidyl ether)

To a 500 milliliter round bottom equipped with an overhead stirrer,nitrogen inlet, reflux condenser, additional funnel, and temperaturecontroller was charged 1.9 grams of ethanol (22 mmoles) and 200 grams ofcyclohexane. The solution was brought to 50° C. Once heated, 0.5milliliters (4 mmoles) of BF₃ /Et₂ O was added using a 2 millilitersyringe. Once the acid was added, 100.0 grams of nonylphenol glycidylether (362 mmoles) was added dropwise so as to maintain a reactiontemperature of 45° C.-55° C. Once the glycidyl ether was added, thesolution is refluxed for 3 hours, then cooled to about 50° C.

While hot (<60° C.) the organic was transferred to a separatory funneland was washed once with 100 milliliters of 5% sodium bicarbonatesolution. The aqueous layer was drained and the organic was washed twomore times with 100 milliliter portions of deionized water. The aqueouslayers were decanted and the organic was dried for at least 1 hour overmagnesium sulfate. Once dry the magnesium sulfate was filtered from theorganic which was stripped of solvent using a rotary evaporator. Thefinal yield of viscous polymer was 100 grams. The GPC molecular weightwas Mw=2600 and the Mn=1700 based on monodisperse polystyrene standards.

EXAMPLE 6 Ethoxylation of Poly(nonylphenol glycidyl ether)

To a 500 milliliter stainless steel Zipperclave was added 60.0 grams(0.035 moles based on an approximate molecular weight of 1700 gram/mole)of the resin prepared in Example 5 along with 0.5 grams of potassiumhydroxide. The vessel was attached to an automated ethoxylation unit andwas heated to 50° C. The vessel was continuously purged with nitrogenfor 15 minutes and was then heated to 100° C. where it was againcontinuously purged with nitrogen for another 15 minutes. The vessel wasthen heated to 140° C. and was given a series of 6 purges by pressuringthe vessel up to 80 psi, and then venting. Once the venting process wascomplete, the vessel was pressured to 20 psi with nitrogen.

The ethylene oxide lines were opened to the motor valves along with themain feed line on the Zipperclave. The feed was continued and the vesselpressure was regulated at 55 psi and a temperature of 140° C. Theautomation was designed to hold the temperature and the pressure withinsafe operating limits while addition of ethylene oxide proceeded througha pair of motor control valves. The feed was allowed to continue until60.0 grams of ethylene oxide (1.362 moles) was added based on adifference weight of the feed cylinder. After the feed was complete, thereaction was allowed to continue for 1 hour after which the vessel wascooled to 60° C., purged 4 times with nitrogen to 80 psi and was dumpedto a container. The final product yield was 115 grams with a theoreticalyield of 120 grams. The GPC molecular weight of the product was Mw=3550and the MN=2930 based on monodisperse polystyrene standards.

EXAMPLE 7 Preparation of Poly(phenyl glycidyl ether)

To a 500 milliliter round bottom equipped with an overhead stirrer,nitrogen inlet, reflux condenser, addition funnel, and temperaturecontroller was charged 47.06 grams of phenol (500 mmoles) and 100 gramsof toluene. The solution was brought to 50° C. Once heated, 1.0milliliter (8 mmoles) of BF₃ /Et₂ O was added using a 2 millilitersyringe. Once the acid was added, 68.18 grams of phenyl glycidyl ether(454 moles) was added dropwise so as to maintain a reaction temperatureof 45° C.-55° C. Once the glycidyl ether was added, the solution isrefluxed for 3 hours, then cooled to about 50° C.

While hot (<60° C.) the organic was transferred to a separatory funneland was washed once with 100 milliliters of 5% sodium bicarbonatesolution. The aqueous layer was drained and the organic was washed twomore times with 100 milliliter portions of deionized water. The aqueouslayers were decanted and the organic was dried for at least 1 hour overmagnesium sulfate. Once dry the magnesium sulfate was filtered from theorganic which was stripped of solvent using a rotary evaporator. Thefinal yield of viscous polymer was 90.3 grams (with 11% unreactedphenol). The GPC molecular weight was Mw=470 and the Mn=310 (on averagea trimer) based on monodisperse polystyrene standards.

EXAMPLE 8 Preparation of 1,3Bis(phenoxy)-2-propanol using the CascadingPolyol Technique

To a 1 liter round bottom flask equipped with an overhead stirrer,nitrogen inlet, reflux condenser, addition funnel, and temperaturecontroller was charged 94.11 grams of phenol (1 mole), 12.86 grams oftetraethylammonium iodide (0.05 moles), 3.00 grams of water (0.17moles), 42.08 grams of potassium hydroxide (0.75 moles), and 250 gramsof toluene. To a 100 milliliter additional funnel was charged 23.13grams of epichlorohydrin (0.25 moles) and 50 grams of toluene. Thesolution was brought to 65° C. at which time the epichlorohydrinsolution was added over a period of 15 minutes while maintaining areaction temperature of 65° C.±5° C. The reaction was allowed to proceedfor 48 hours.

After 48 hours, the solution was cooled down to room temperature. Thetoluene solution was washed with two 250 milliliters portions ofdeionized water. The aqueous layers were drained off, and the toluenewas removed along with unreacted phenol using a rotary evaporator. Thefinal yield of product was 64.5 grams which was 106% of theory (residualis phenol). Final product purity was about 95% as shown by GPC.

EXAMPLE 9 Dimerization of 1,3-Bis(phenoxy)-2-propanol using theCascading Polyol Technique

To a 250 milliliter round bottom flask equipped with an overheadstirrer, nitrogen inlet, reflux condenser, additional funnel, andtemperature controller was charged 20.03 grams of1,3-bis-(phenoxy)-2-propanol prepared in Example 8 (82 mmoles), 2.06grams of tetraethylammonium iodide (8 mmoles), 0.49 grams of water (27mmoles), 6.51 grams of potassium hydroxide (116 mmoles), and 125 gramsof toluene. To a 100 milliliter addition funnel was charged 3.61 gramsof epichlorohydrin (39 mmoles) and 25 grams of toluene. The solution wasbrought to 65° C. at which time the epichlorohydrin solution was addedover a period of 15 minutes while maintaining a reaction temperature of65° C.±5° C. The reaction was allowed to proceed for 48 hours.

After 48 hours, the solution was cooled down to room temperature. Thetoluene solution was washed with two 250 milliliter portions ofdeionized water. The aqueous layers were drained off, and the toluenewas removed using a rotary evaporator. The final yield of product was21.6 grams which was 101% of theory. GPC showed two major components ofthe product. The first was the starting material at about 41% (Mn=220)and the second was the coupled product at about 59% (Mn=520).

EXAMPLE 10 Preparation of 1,3-Bis(hexadecyloxy)-2-propanol using theCascading Polyol Technique

To a 500 milliliter round bottom flask equipped with an overheadstirrer, nitrogen inlet, reflux condenser, additional funnel, andtemperature controller was charged 60.61 grams of hexadecanol (0.25moles), 6.18 grams of tetraethylammonium iodide (0.024 moles), 1.44grams of water (0.082 moles), 20.20 grams of potassium hydroxide (0.36moles), and 125 grams of toluene. To a 100 milliliter addition funnelwas charged 11.10 grams of epichlorohydrin (0.12 moles) and 25 grams oftoluene. The solution was brought to 65° C. at which time theepichlorohydrin solution was added over a period of 15 minutes whilemaintaining a reaction temperature of 65° C.±5° C. The reaction wasallowed to proceed for 48 hours.

After 48 hours, the solution was cooled down to room temperature. Thetoluene solution was washed with two 250 milliliter portions ofdeionized water. The aqueous layers were drained off, and the toluenewas removed using a rotary evaporator. The final yield of product was70.9 grams which is 109% of theory (residual is hexadecanol).

EXAMPLE 11 Sulfation of1,3-Bis(nonylphenoxy)-2-propanol-block-(propylene oxide)₁₀-block-(ethylene oxide)₁₀

To a 250 milliliter round bottom flask equipped with an overheadstirrer, a temperature controller, and a vacuum adapter was added 75.0grams of the material from Example 13 (49 mmoles). The kettle was thenevacuated to <20 mmHg and heated to 100° C. to remove any water. After 1hour, the kettle was cooled to 60° C. while under vacuum. When reaching60° C., vacuum was broken with nitrogen and 5.3 grams of sulfamic acid(54 mmoles) was added. After charging the sulfamic acid, the kettle washeated to 110° C. and evacuated to <20 mmHg. The reaction was allowed toproceed for 3 hours.

At the end of the hold period, the kettle was cooled to 85° C. andvacuum was broken with nitrogen. 1.2 grams of diethanolamine (11 mmoles)was slowly added under a blanket of nitrogen. This solution was stirredfor 30 minutes. 10 grams of ethanol was added to the kettle and thetemperature was regulated to 55° C. This solution was stirred for 30minutes. The heat was removed from the kettle and 30 grams of wateralong with 20 grams of ethanol were added while maintaining goodagitation. The solution was stirred for 15 minutes or until cooled toroom temperature (<35° C.).

The pH was checked by dissolving 2 grams of the product solution in 18grams of deionized water. If the pH was below 6.5, 0.2 gram incrementsof diethanolamine was added until the pH is between 6.5 and 7.5.

EXAMPLE 12 Preparation of1,3-Bis(nonylphenoxy)-2-propanol-block-(propylene oxide)₁₀

To a 500 milliliter stainless steel Zipperclave was added 100.0 grams(0.202 moles) of 1,3-bis(nonylphenoxy)-2-propanol prepared in Example 1along with 0.7 grams of potassium hydroxide. The vessel was attached toan automated unit and was heated to 50° C. The vessel was continuouslypurged with nitrogen for 15 minutes and was then heated to 100° C. whereit was again continuously purged with nitrogen for another 15 minutes.The vessel was then heated to 140° C. and is given a series of 6 purgesby pressuring the vessel up to 80 psi, and then venting. Once theventing process was completed, the vessel was pressured to 20 psi withnitrogen.

Lines connected to a cylinder which had been precharged with 117.0 gramsof propylene oxide (2.02 moles) were opened to the motor valves alongwith the main feed line on the Zipperclave. The feed was continued andthe vessel pressure was regulated at 55 psi and a temperature of 140° C.The automation was designed to hold the temperature and the pressurewithin safe operating limits while addition of ethylene oxide proceededthrough a pair of motor control valves. The feed was allowed to continueuntil all of the propylene oxide had been fed. After the feed wascomplete, the reaction was allowed to continue for 1 hour after whichthe vessel was cooled to 60° C., purged 4 times with nitrogen to 80 psiand was dumped to a container. The final product yield was 211 gramswith a theoretical yield of 277 grams. The GPC molecular weight of theproduct was Mw=650 and the Mn=490 based on monodisperse polystyrenestandards.

EXAMPLE 13 Preparation of1,3-Bis(nonylphenoxy)-2-propanol-block-(propylene oxide)₁₀-block-(ethylene oxide)₁₀

To a 500 milliliter stainless steel Zipperclave was added 75.0 grams ofthe propoxylate prepared in Example 12 (0.070 moles) along with 0.3grams of potassium hydroxide. The vessel was attached to an automatedethoxylation unit and was heated to 50° C. The vessel was continuouslypurged with nitrogen for 15 minutes and was then heated to 100° C. whereit was again continuously purged with nitrogen for another 15 minutes.The vessel was then heated to 140° C. and was given a series of 6 purgesby pressuring the vessel up to 80 psi, and then venting. Once theventing process was completed, the vessel was pressured to 20 psi withnitrogen.

The ethylene oxide lines were opened to the motor valves along with themain feed line on the Zipperclave. The feed was continued and the vesselpressure was regulated at 55 psi and a temperature of 140° C. Theautomation was designed to hold the temperature and the pressure withinsafe operating limits while addition of ethylene oxide proceeded througha pair of motor control valves. The feed was allowed to continue until30.7 grams ethylene oxide (0.696 moles) was added based on a differenceweight of the feed cylinder. After the feed was complete, the reactionis allowed to continue for 1 hour after which the vessel was cooled to60° C., purged 4 times with nitrogen to 80 psi and was dumped to acontainer. The final product yield was 99 grams with a theoretical yieldof 106 grams.

EXAMPLE 14 Preparation of Bis(nonylphenoxy) Adduct of 1,4-ButanediolDiglycidyl Ether

To a five neck, two liter round bottom flask equipped with an additionfunnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and adecanting head with a water-cooled condenser were added 506.8 grams(2.30 mole) of nonylphenol and 350 milliliters of cyclohexane. Thesolution was heated to reflux, and 6.5 grams (1.3 weight percent basedon nonylphenol) of potassium hydroxide in 15 milliliters of water wasslowly added to the round bottom flask. After all the water wasrecovered in the decanting head (15 milliliters+2 milliliters formed),220 grams (1.09 mole) of 1,4-butanediol diglycidyl ether was addeddropwise between 60 and 80° C. After the addition was complete, thesolution was refluxed for four hours. The contents of the flask werethen washed with a five percent aqueous solution of phosphoric acid, andthe organic layer was separated from the water layer and washed twicewith deionized water. The reaction mixture was then placed in a oneliter round bottom flask, and the remaining cyclohexane and unreactednonylphenol were recovered by distillation, first at atmosphericpressure, then under vacuum at 0.2 mm Hg. The kettle temperature was notallowed to exceed 180° C. during the distillation to preventdiscoloration of the product. The concentrated solution was thenrefiltered to give 710 grams of a pale-yellow liquid. Molecular weightby end-group MW analysis was 689.9 (theoretical MW= 643.0). Ir and nmrspectra were consistent with the expected structure of the product.

EXAMPLE 15 Preparation of 3 Mole Ethoxylate of1,3-Bis(nonylphenoxy)-2-propanol

To a five hundred milliliter Zipperclave reactor were charged, undernitrogen, 200.1 grams (0.43 mole) of 1,3-bis(nonylphenoxy)-2-propanolprepared in Example 2 and 0.20 grams (0.1 weight percent) of BF₃ ·Et₂ O.The reaction mixture was heated to 80° C., and 55.1 grams (1.25 mole) ofethylene oxide was fed to the reactor over a two hour period. After allthe ethylene oxide was fed, the reaction mixture was allowed to cook outfor one hour and then dumped hot, under nitrogen, into a jar containing160 milliliters of a one percent aqueous solution of sodium hydroxide.The organic layer was separated from the water layer and washed twicewith deionized water. The washes were performed at 90° C. to facilitatethe separation of the two layers. The product was then dried byazeotropic removal of the water, using cyclohexane (300 milliliters) asthe entrainer. The cyclohexane was stripped off under vacuum to give apale-yellow liquid with a molecular weight by end-group MW analysis of601.7 (theoretical MW=629). Ir and nmr spectra were consistent with theexpected structure of the product.

EXAMPLE 16 Preparation of 8 Mole Ethoxylate of Bis(nonylphenoxy) Adductof 1,4-Butanediol Diglycidyl Ether

To a five hundred milliliter Zipperclave reactor were charged, undernitrogen, 150.2 grams (0.22 mole) of bis(nonylphenoxy) adduct of1,4-butanediol diglycidyl ether prepared in Example 14 and 0.30 grams(0.2 weight percent) of BF₃ ·Et₂ O. The reaction mixture was heated to80° C., and 77.5 grams (1.76 mole) of ethylene oxide was fed to thereactor over a two hour period. After all the ethylene oxide was fed,the reaction mixture was allowed to cook out for one hour and thendumped hot, under nitrogen, into a jar containing 160 milliliters of aone percent aqueous solution of sodium hydroxide. The organic layer wasseparated from the water layer and washed twice with deionized water.The washes were performed at 90° C. to facilitate the separation of thetwo layers. The product was then dried by azeotropic removal of thewater, using cyclohexane (300 milliliters) as the entrainer. Thecyclohexane was stripped off under vacuum to give a pale-yellow liquidwith a molecular weight by end-group MW analysis of 1047 (theoreticalMW=995). Ir and nmr spectra were consistent with the expected structureof the product.

EXAMPLE 17 Preparation of Macromonomer Compound

Into a 1 liter round bottom reaction flask equipped with a heatingmantle, dean stark trap, condenser, thermometer, nitrogen bubbler,nitrogen purge line and stirrer was charged 300 grams of toluene and 63grams of a surfactant identified as S-1 in Table A below. With nitrogenpurge, the resulting solution was heated to reflux at approximately 110°C. and azeotroped to remove trace water to dryness. The solution wassubsequently cooled to 90° C., and 1.5 grams of bismuth hex chem 8%bismuth octoate catalyst (Mooney Chemical, Inc., Cleveland, Ohio) wascharged and allowed to mix well, after which a stoichiometric amount of95% m-TMI aliphatic isocyanate (American Cyanamid, Stamford,Connecticut) was charged. After the reaction proceeded at 90° C. for 1.3hours, the resulting product was cooled to 70° C. and 0.03 grams of2,6-di-tert-4-methyl phenol (BHT) preservative was added. The mixturewas poured into a stainless steel pan with large surface area tofacilitate drying. The final product was a waxy material, and isdesignated herein as macromonomer M-1.

                  TABLE A                                                         ______________________________________                                         ##STR15##                                                                                                     Moles of                                     Surfactant                                                                            R.sub.1     R.sub.2 /R.sub.3                                                                           Ethoxylation                                 ______________________________________                                        S-1     Nonylphenol Hydrogen (R.sub.2)                                                                         40                                           S-2     Nonylphenol Nonylphenol (R.sub.3)                                                                      40                                           S-3     Nonylphenol Nonylphenol (R.sub.3)                                                                      20                                           S-4     Nonylphenol Octylphenol (R.sub.3)                                                                      20                                           S-5     Nonylphenol Octylphenol (R.sub.3)                                                                      40                                           S-6     Nonylphenol Nonylphenol (R.sub.3)                                                                      80                                           S-7     Nonylphenol Nonylphenol (R.sub.3)                                                                      120                                          ______________________________________                                    

EXAMPLES 18-34 Preparation of Macromonomer Compounds

In a manner similar to that described in Example 17, other macromonomerswere prepared using stoichiometric amounts of the surfactants andunsaturated compounds identified in Table B below.

                  TABLE B                                                         ______________________________________                                        Example          Unsaturated     Macromonomer                                 No.    Surfactant                                                                              Compound        Designation                                  ______________________________________                                        18     S-2       m-TMI           M-2                                          19     S-3       m-TMI           M-3                                          20     S-4       m-TMI           M-4                                          21     S-5       m-TMI           M-5                                          22     S-6       m-TMI           M-6                                          23     S-7       m-TMI           M-7                                          24     S-2       Isocyanato Ethyl                                                                              M-8                                                           Methacrylate                                                 25     S-5       Isocyanato Ethyl                                                                              M-9                                                           Methacrylate                                                 26     S-1       Methacrylic Anhydride                                                                         M-10                                         27     S-2       Methacrylic Anhydride                                                                         M-11                                         28     S-5       Methacrylic Anhydride                                                                         M-12                                         29     S-6       Methacrylic Anhydride                                                                         M-13                                         30     S-2       Acrylic Anhydride                                                                             M-14                                         31     S-5       Acrylic Anhydride                                                                             M-15                                         32     S-6       Acrylic Anhydride                                                                             M-16                                         33     S-2       Crotonic Anhydride                                                                            M-17                                         34     S-5       Maleic Anhydride                                                                              M-18                                         ______________________________________                                    

EXAMPLE 35 Preparation of Alkali Soluble Thickener

A monomer mixture (300 grams) was prepared by charging ethyl acrylate(Aldrich), methacrylic acid (Aldrich), macromonomer M-1, 13 grams of a75% solution of Aerosol® OT surfactant (American Cyanamid, Stamford,Conn.), and 3 grams of distilled deionized water to a bottle, anddispersing the contents with vigorous shaking. The ethyl acrylate,methacrylic acid and macromonomer M-1 were added in amounts identifiedin Table C below. A catalyst feed mixture comprised of 0.53 grams ofsodium persulfate (Aldrich) and 52.47 grams of water was prepared inanother container. To a 2 liter resin flask that had been immersed in athermostated water bath and equipped with a 4-bladed stainless steelmechanical stirrer, Claisen connecting tube, water condenser, nitrogensparge and bubble trap, thermometer and monomer and catalyst additioninlets, 1.20 grams of the sodium salt of vinyl sulfonic acid and 658.5grams of water were charged. The monomer mixture was charged to a1-liter graduated monomer feed cylinder, and the catalyst solution wascharged to a 125 milliliter graduated catalyst feed cylinder. Undernitrogen purge, the reactor was heated to 70° C., whereupon 33milliliters of the monomer mixture and 3 milliliters of the catalystfeed mixture were charged to the reaction vessel. The reaction vesselwas subsequently heated to 80° C. After allowing the monomers to reactfor 20 minutes to form a seed product, the monomer and catalyst feedmixtures were conveyed to the reaction vessel by FMI pumps via 1/8"teflon tubing at a rate of 1.94 and 0.27 milliliters/minute,respectively, under continuous stirring at a reaction temperature heldbetween 76°-82° C. The reaction was allowed to proceed for another hour,after which the product was cooled and filtered with a 200 mesh nyloncloth. The coagulum was collected from the reaction vessel and filtercloth. Thickening ability of the resulting product was monitored byBrookfield viscosity at 6 rpm by diluting the latex to 0.25%, 0.50% and0.75% solids, and subsequently neutralizing the product to pH=9.0 with a95% solution of 2-amino-2-methyl-1-propanol (AMP-95, Angus ChemicalCompany). The results are given in Table C.

EXAMPLES 36-131 Preparation of Alkali Soluble Thickeners

In a manner similar to that described in Example 35, other alkalisoluble thickeners were prepared using the monomers identified in TablesC-J below in the amounts identified in Tables C-J. Table C illustratesthe influence of m-TMI-containing macromonomer concentration andethoxylation on thickening efficiency. Table D illustrates the influenceof mixing m-TMI-containing macromonomers of various ethoxylations onthickening efficiency. Table E illustrates the influence of unsaturationtype of urethane-containing macromonomers on thickening efficiency.Table F illustrates the influence of macromonomer ester structure andethoxylation on thickening efficiency. Table G illustrates the influenceof acid type and concentration on thickening efficiency. Table Hillustrates the influence of polymer glass transition temperature andwater solubility on thickening efficiency. Table I illustrates theinfluence of cross-linkable monomer concentration on thickeningefficiency. Table J illustrates the influence of mercaptan on thickeningefficiency. As used in Tables C-J below, the following abbreviationshave the indicated meanings: MM=Macromonomer; EA=Ethyl Acrylate;MAA=Methacrylic Acid; AA=Acrylic Acid; MA=Methyl Acrylate; t-BA=t-ButylAcrylate; n-BA=n-Butyl Acrylate; MMA=Methyl Methacrylate;2-EHP=2-Ethylhexyl Propionate Mercaptan; and 2-HEA=2-Hydroxy EthylAcrylate.

                                      TABLE C                                     __________________________________________________________________________                 Thickener Composition by                                                                  Brookfield Viscosity                                              Weight      (CPS) @ pH = 9.0                                                                           Thickener                               Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                             0.25%                                                                             0.50%                                                                             0.75%                                                                              Designation                             __________________________________________________________________________    35   M-1     10  50  40   90   380                                                                              1,000                                                                             P-1                                     36   M-2      5  55  40  270 11,400                                                                            103,600                                                                            P-2                                     37   M-2     10  50  40  120  3,100                                                                            60,000                                                                             P-3                                     38   M-2     10  50  40  105 10,400                                                                            130,000                                                                            P-3a                                    39   M-2     20  40  40   25  2,150                                                                            50,500                                                                             P-4                                     40   M-2     30  30  40   10   790                                                                             20,000                                                                             P-5                                     41   M-3      5  55  40  390  2,260                                                                            17,900                                                                             P-6                                     42   M-3       6.5                                                                               53.5                                                                            40  142  1,200                                                                            18,500                                                                             P-7                                     43   M-3     10  50  40  220  3,050                                                                            40,000                                                                             P-8                                     44   M-3     20  40  40   75  2,350                                                                            27,500                                                                             P-9                                     45   M-4     10  50  40  242  4,400                                                                            39,000                                                                             P-10                                    46   M-5     10  50  40   45  7,400                                                                            84,000                                                                             P-11                                    47   M-5     20  40  40   34  4,450                                                                            59,000                                                                             P-12                                    48   M-6      5  55  40  460 25,500                                                                            88,000                                                                             P-13                                    49   M-6     10  50  40  105 39,000                                                                            150,000                                                                            P-14                                    50   M-6     15  45  40  195 43,000                                                                            140,000                                                                            P-15                                    51   M-6     20  40  40  125 52,500                                                                            187,000                                                                            P-16                                    52   M-6     30  30  40  315 56,500                                                                            162,000                                                                            P-17                                    53   M-7      5  55  40  230  7,800                                                                            15,800                                                                             P-18                                    54   M-7     10  50  40  900 17,400                                                                            35,000                                                                             P-19                                    __________________________________________________________________________

                                      TABLE D                                     __________________________________________________________________________                 Thickener Composition by                                                                  Brookfield Viscosity                                              Weight      (CPS) @ pH = 9.0                                                                           Thickener                               Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                             0.25%                                                                             0.50%                                                                             0.75%                                                                              Designation                             __________________________________________________________________________    55   M-3:M-6 10  50  40  225 24,000                                                                             85,000                                                                            P-20                                         1:1                                                                      56   M-2:M-6 10  50  40  135 21,200                                                                            134,000                                                                            P-21                                         1:1                                                                      __________________________________________________________________________

                                      TABLE E                                     __________________________________________________________________________                 Thickener Composition by                                                                  Brookfield Viscosity                                              Weight      (CPS) @ pH = 9.0                                                                           Thickener                               Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                             0.25%                                                                             0.50%                                                                             0.75%                                                                              Designation                             __________________________________________________________________________    57   M-8      5  55  40  250 14,800                                                                            124,000                                                                            P-22                                    58   M-8     10  50  40  93  11,200                                                                            125,400                                                                            P-23                                    59   M-8     20  40  40  45  6,140                                                                             84,500                                                                             P-24                                    60   M-9      5  55  40  275 6,200                                                                             57,000                                                                             P-25                                    61   M-9     10  50  40  250 10,100                                                                            80,000                                                                             P-26                                    62   M-9     20  40  40  90  7,800                                                                             90,000                                                                             P-27                                    63   M-9     30  30  40  45  5,200                                                                             69,000                                                                             P-28                                    __________________________________________________________________________

                                      TABLE F                                     __________________________________________________________________________                 Thickener Composition by                                                                  Brookfield Viscosity                                              Weight      (CPS) @ pH = 9.0                                                                            Thickener                              Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                             0.25%                                                                              0.50%                                                                             0.75%                                                                              Designation                            __________________________________________________________________________    64   M-10    10  50  40  130    285                                                                                410                                                                             P-29                                   65   M-11    10  50  40  190  19,500                                                                            152,000                                                                            P-30                                   66   M-11    20  40  40  120  13,500                                                                            146,000                                                                            P-31                                   67   M-11    30  30  40   96   8,000                                                                             73,000                                                                            P-32                                   68   M-12     5  55  40  260   5,400                                                                             51,000                                                                            P-33                                   69   M-12    10  50  40  175   9,200                                                                             71,000                                                                            P-34                                   70   M-12    20  40  40  100   7,400                                                                             77,000                                                                            P-35                                   71   M-12    30  30  40   62   4,500                                                                             63,000                                                                            P-36                                   72   M-13     5  55  40  320  25,600                                                                             79,000                                                                            P-37                                   73   M-13    10  50  40   97  28,000                                                                            125,000                                                                            P-38                                   74   M-13    20  40  40  300  58,200                                                                            171,000                                                                            P-39                                   75   M-13    30  30  40  730  63,000                                                                            163,000                                                                            P-40                                   76   M-14    10  50  40  410  22,700                                                                            130,000                                                                            P-41                                   77   M-14    20  40  40  1225 44,500                                                                            168,000                                                                            P-42                                   78   M-14    30  30  40  1010 42,500                                                                            180,000                                                                            P-43                                   79   M-15     5  55  40   84   1,680                                                                             29,000                                                                            P-44                                   80   M-15    10  50  40  350  12,000                                                                             83,000                                                                            P-45                                   81   M-15    20  40  40  220  24,500                                                                            122,000                                                                            P-46                                   82   M-15    30  30  40  1050 33,000                                                                            133,000                                                                            P-47                                   83   M-16     5  55  40  450  17,720                                                                             45,300                                                                            P-48                                   84   M-16    10  50  40  1,345                                                                              27,000                                                                             98,000                                                                            P-49                                   85   M-16    20  40  40  3,450                                                                              65,800                                                                            158,000                                                                            P-50                                   86   M-16    30  30  40  11,600                                                                             81,000                                                                            157,000                                                                            P-51                                   87   M-17    10  50  40  410  12,000                                                                             60,000                                                                            P-52                                   88   M-17    20  40  40  255  10,600                                                                             46,300                                                                            P-53                                   89   M-17    30  30  40   38   2,525                                                                             13,500                                                                            P-54                                   90   M-18     5  55  40  100    810                                                                              3,500                                                                             P-55                                   91   M-18    10  50  40  110   1,420                                                                             5,940                                                                             P-56                                   92   M-18    20  40  40   30    870                                                                              2,425                                                                             P-57                                   __________________________________________________________________________

                                      TABLE G                                     __________________________________________________________________________                 Thickener Composition by                                                                      Brookfield Viscosity                                          Weight          (CPS) @ pH = 9.0                                                                           Thickener                           Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                             % AA                                                                              0.25%                                                                             0.50%                                                                             0.75%                                                                              Designation                         __________________________________________________________________________    93   M-2     10  60  30  0   1520                                                                              12,200                                                                            102,000                                                                            P-58                                94   M-2     10  70  20  0    45  3,800                                                                            50,000                                                                             P-59                                95   M-2     10  80  10  0   <10   <10                                                                               <10                                                                              P-60                                96   M-2     10  60   0  30  <10    95                                                                              6,800                                                                             P-61                                97   M-6     20  60  20  0    15 13,500                                                                            43,500                                                                             P-62                                98   M-6      5  65  30  0    210                                                                              13,000                                                                            56,500                                                                             P-63                                99   M-6     10  60  30  0    77 24,000                                                                            88,000                                                                             P-64                                100  M-6     20  50  30  0    17  7,600                                                                            79,000                                                                             P-65                                101  M-6      5  45  50  0    130                                                                               7,060                                                                            28,000                                                                             P-66                                102  M-6     10  40  50  0    86 16,700                                                                            52,500                                                                             P-67                                103  M-6     20  30  50  0    130                                                                              28,000                                                                            122,000                                                                            P-68                                104   M-11   10  70   0  20  <10   213                                                                               7300                                                                             P-69                                105   M-17   10  50  20  20   710                                                                              16,500                                                                            66,000                                                                             P-70                                __________________________________________________________________________

                                      TABLE H                                     __________________________________________________________________________                 Thickener Composition by                                                                       Brookfield Viscosity                                         Weight           (CPS) @ pH = 9.0                                                                           Thickener                          Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                             % Other                                                                            0.25%                                                                             0.50%                                                                             0.75%                                                                              Designation                        __________________________________________________________________________    106  M-2     10  40  40  10   90  5,760                                                                             82,000                                                                             P-71                                                        MMA                                                  107  M-2     10  30  40  20   15  1,125                                                                             55,000                                                                             P-72                                                        MMA                                                  108  M-2     10  20  40  30   10    207                                                                              6,000                                                                             P-73                                                        MMA                                                  109  M-2     10   0  40  50   <10  <10                                                                                <10                                                                              P-74                                                        MMA                                                  110  M-2     10  30  40  20   20    310                                                                              1,330                                                                             P-75                                                        styrene                                              111  M-2     10  40  40  10   95  7,540                                                                             75,500                                                                             P-76                                                        styrene                                              112  M-2     10  40  40  10   220 13,800                                                                            118,000                                                                            P-77                                                        n-BA                                                 113  M-2     10  30  40  20   185 7,400                                                                             66,500                                                                             P-78                                                        n-BA                                                 114  M-2     10  40  40  10   130 10,100                                                                            100,000                                                                            P-79                                                        t-BA                                                 115  M-2     10  30  40  20   125 7,200                                                                             77,500                                                                             P-80                                                        t-BA                                                 116  M-2     10  40  40  10   100 6,900                                                                             121,000                                                                            P-81                                                        MA                                                   117  M-2     10  30  40  20   73  5,000                                                                             90,000                                                                             P-82                                                        MA                                                   118  M-6     20  30  40  10   33  15,400                                                                            150,000                                                                            P-83                                                        MMA                                                  __________________________________________________________________________

                                      TABLE I                                     __________________________________________________________________________                 Thickener Composition                                                                            Brookfield Viscosity                                       by Weight          (CPS) @ pH = 9.0                                                                           Thickener                        Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                              % 2-HEA                                                                             0.25%                                                                             0.50%                                                                             0.75%                                                                              Designation                      __________________________________________________________________________    119  M-2     10  47.7                                                                              40   2.3   97  9,060                                                                             127,000                                                                            P-84                             120  M-2     10  57.7                                                                              30   2.3   62  6,300                                                                             76,000                                                                             P-85                             121  M-2     20  37.5                                                                              40   2.5   27  6,200                                                                             116,600                                                                            P-86                             122  M-2     20  35  40   5     <10   260                                                                             18,600                                                                             P-87                             123  M-2     20  32.5                                                                              40   7.5   20    720                                                                             40,000                                                                             P-88                             124  M-2     20  30  40   10    10    520                                                                             29,500                                                                             P-89                             __________________________________________________________________________

                                      TABLE J                                     __________________________________________________________________________                 Thickener Composition                                                                            Brookfield Viscosity                                       by Weight          (CPS) @ pH = 9.0                                                                           Thickener                        Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                              % 2-HEP*                                                                            0.25%                                                                             0.50%                                                                             0.75%                                                                              Designation                      __________________________________________________________________________    125  M-2     10  40  50    .05   165                                                                              22,800                                                                            142,000                                                                            P-90                             126  M-2     10  50  40   0.2    18  2,060                                                                            66,500                                                                             P-91                             127  M-2     10  50  40   0.3   <10   115                                                                              9,700                                                                             P-92                             128  M-2     10  50  40   0.5   <10    12                                                                               355                                                                              P-93                             129  M-2     10  50  40   1     <10   <10                                                                               <10                                                                              P-94                             130  M-6     10  50  40    .05   230                                                                              23,700                                                                            90,700                                                                             P-95                             131  M-6     10  50  40    .2    30  5,170                                                                            33,000                                                                             P-96                             __________________________________________________________________________     *% charged to reactor based on monomer.                                  

EXAMPLES 132-187 Co-Thickening with Surfactants

The addition of certain surfactants to an associative polymer solutionproduces a co-thickening effect. The results in Table L below show theco-thickening effect produced by the addition with thorough mixing ofcertain surfactants identified in Table K below in the amountsidentified in Table L to a 0.5% alkaline solution of an alkali solublethickener identified in Table L as measured with a Brookfield Viscometerat 6 rpm at pH=9.0.

                  TABLE K                                                         ______________________________________                                         ##STR16##                                                                                                     Moles of                                     Surfactant                                                                            R.sub.1     R.sub.2 /R.sub.3                                                                           Ethoxylation                                 ______________________________________                                        S-8     Nonylphenol Nonylphenol (R.sub.3)                                                                      20                                           S-9     Nonylphenol Nonylphenol (R.sub.3)                                                                      40                                           S-10    Nonylphenol Nonylphenol (R.sub.3)                                                                      80                                           S-11    Nonylphenol Hydrogen (R.sub.2)                                                                         25                                           S-12    Nonylphenol Hydrogen (R.sub.2)                                                                         40                                           S-13    Nonylphenol Octylphenol (R.sub.3)                                                                      20                                           S-14    Nonylphenol Octylphenol (R.sub.3)                                                                      40                                            S-15*  Nonylphenol Nonylphenol (R.sub.3)                                                                      40                                           S-16    Octylphenol Hydrogen (R.sub.2)                                                                         25                                           ______________________________________                                         *Sulfated derivative.                                                    

                  TABLE L                                                         ______________________________________                                                      Surfactant                                                      Ex-   Sur-    Concentration                                                                             Thick- Brookfield Viscosity                         ample factant (wt. %)     ener   (cps) @ pH = 9.0                             ______________________________________                                        132   S-8     0.0         P-3    3100                                               S-8     0.2         P-3    32700                                              S-8     0.4         P-3    45700                                              S-8     0.8         P-3    63300                                              S-8     1.0         P-3    65500                                              S-8     2.0         P-3    >100000                                      133   S-9     0.2         P-3    24200                                              S-9     0.4         P-3    18700                                              S-9     0.8         P-3    6600                                               S-9     1.0         P-3    4060                                                       2.0         P-3    1225                                         134   S-10    0.2         P-3    20600                                              S-10    0.4         P-3    17300                                              S-10    0.8         P-3    8500                                               S-10    1.0         P-3    6300                                               S-10    2.0         P-3    1850                                         135   S-11    0.2         P-3    12000                                              S-11    0.4         P-3    3160                                               S-11    0.8         P-3     700                                               S-11    1.0         P-3     485                                               S-11    2.0         P-3     480                                         136   S-12    0.2         P-3    9200                                               S-12    0.4         P-3    4500                                               S-12    0.8         P-3    1000                                               S-12    1.0         P-3     875                                               S-12    2.0         P-3     565                                         137   S-13    0.2         P-3    34300                                              S-13    0.4         P-3    26700                                              S-13    0.8         P-3    11500                                              S-13    1.0         P-3    8600                                               S-13    2.0         P-3    2450                                         138   S-14    0.2         P-3    22200                                              S-14    0.4         P-3    17200                                              S-14    0.8         P-3    6900                                               S-14    1.0         P-3    4500                                               S-14    2.0         P-3    1500                                         139   S-15    0.2         P-3    10500                                              S-15    0.4         P-3    4940                                               S-15    0.8         P-3    2160                                               S-15    1.0         P-3    1450                                               S-15    2.0         P-3     355                                         140   S-16    0.2         P-3    14300                                              S-16    0.4         P-3    4080                                               S-16    0.8         P-3    1075                                               S-16    1.0         P-3     735                                               S-16    2.0         P-3     485                                         141   S-8     0.0         P-2    11400                                              S-8     0.2         P-2    23500                                              S-8     0.4         P-2    34000                                              S-8     0.8         P-2    64000                                              S-8     1.0         P-2    71000                                              S-8     2.0         P-2    93000                                        142   S-9     0.2         P-2    11000                                              S-9     0.4         P-2    4000                                               S-9     0.8         P-2    2000                                               S-9     1.0         P-2    1400                                               S-9     2.0         P-2     850                                         143   S-10    0.2         P-2    10500                                              S-10    0.4         P-2    5000                                               S-10    0.8         P-2    2000                                               S-10    1.0         P-2    1600                                               S-10    2.0         P-2     950                                         144   S-11    0.2         P-2    2700                                               S-11    0.4         P-2    1000                                               S-11    0.8         P-2     800                                               S-11    1.0         P-2     660                                               S-11    2.0         P-2     620                                         145   S-12    0.2         P-2    2800                                               S-12    0.4         P-2    1000                                               S-12    0.8         P-2     850                                               S-12    1.0         P-2     660                                               S-12    2.0         P-2     650                                         146   S-8     0.0         P-4    2150                                               S-8     0.2         P-4    19000                                              S-8     0.4         P-4    31000                                              S-8     0.8         P-4    55000                                              S-8     1.0         P-4    61000                                              S-8     2.0         P-4    85000                                        147   S-9     0.2         P-4    19500                                              S-9     0.4         P-4    21500                                              S-9     0.8         P-4    11500                                              S-9     1.0         P-4    7400                                               S-9     2.0         P-4    2250                                         148   S-10    0.2         P-4    12600                                              S-10    0.4         P-4    17400                                              S-10    0.8         P-4    12600                                              S-10    1.0         P-4    6600                                               S-10    2.0         P-4    2600                                         149   S-11    0.2         P-4    17400                                              S-11    0.4         P-4    7800                                               S-11    0.8         P-4    1650                                               S-11    1.0         P-4     860                                               S-11    2.0         P-4     560                                         150   S-12    0.2         P-4    14600                                              S-12    0.4         P-4    7800                                               S-12    0.8         P-4    1500                                               S-12    1.0         P-4     960                                               S-12    2.0         P-4     450                                         151   S-8     0.0         P-5     790                                               S-8     0.2         P-5    4600                                               S-8     0.4         P-5    19600                                              S-8     0.8         P-5    42000                                              S-8     1.0         P-5    50000                                              S-8     2.0         P-5    90000                                        152   S-9     0.2         P-5    5800                                               S-9     0.4         P-5    13200                                              S-9     0.8         P-5    9200                                               S-9     1.0         P-5    5200                                               S-9     2.0         P-5    1600                                         153   S-10    0.2         P-5    4050                                               S-10    0.4         P-5    10400                                              S-10    0.8         P-5    9400                                               S-10    1.0         P-5    5000                                               S-10    2.0         P-5    1600                                         154   S-11    0.2         P-5    10600                                              S-11    0.4         P-5    4200                                               S-11    0.8         P-5    1400                                               S-11    1.0         P-5     970                                               S-11    2.0         P-5     410                                         155   S-12    0.2         P-5    6000                                               S-12    0.4         P-5    4200                                               S-12    0.8         P-5    1150                                               S-12    1.0         P-5     600                                               S-12    2.0         P-5     340                                         156   S-8     0           P-7    1200                                               S-8     0.2         P-7    9000                                               S-8     0.4         P-7    21000                                              S-8     0.8         P-7    37000                                              S-8     1.0         P-7    49000                                              S-8     2.0         P-7    78000                                        157   S-9     0.2         P-7    1600                                               S-9     0.4         P-7    1350                                               S-9     0.8         P-7     900                                               S-9     1.0         P-7     762                                               S-9     2.0         P-7     565                                         158   S-10    0.2         P-7    1100                                               S-10    0.4         P-7    1150                                               S-10    0.8         P-7     900                                               S-10    1.0         P-7     823                                               S-10    2.0         P-7     650                                         159   S-11    0.2         P-7    1175                                               S-11    0.4         P-7     685                                               S-11    0.8         P-7     503                                               S-11    1.0         P-7     495                                               S-11    2.0         P-7     502                                         160   S-12    0.2         P-7     950                                               S-12    0.4         P-7     675                                               S-12    0.8         P-7     525                                               S-12    1.0         P-7     500                                               S-12    2.0         P-7     480                                         161   S-8     0.0          P-13  25500                                              S-8     0.2          P-13  31500                                              S-8     0.4          P-13  46500                                              S-8     0.8          P-13  60000                                              S-8     1.0          P-13  60000                                              S-8     2.0          P-13  62500                                        162   S-9     0.2          P-13  8640                                               S-9     0.4          P-13  2940                                               S-9     0.8          P-13  1200                                               S-9     1.0          P-13  1000                                               S-9     2.0          P-13   750                                         163   S-10    0.2          P-13  10100                                              S-10    0.4          P-13  4200                                               S-10    0.8          P-13  1450                                               S-10    1.0          P-13  1300                                               S-10    2.0          P-13   900                                         164   S-12    0.2          P-13  2540                                               S-12    0.4          P-13  1125                                               S-12    0.8          P-13   750                                               S-12    1.0          P-13   670                                               S-12    2.0          P-13   610                                         165   S-8     0.0          P-14  39000                                              S-8     0.2          P-14  61000                                              S-8     0.4          P-14  73500                                              S-8     0.8          P-14  87000                                              S-8     1.0          P-14  93500                                              S-8     2.0          P-14  122000                                       166   S-9     0.2          P-14  41000                                              S-9     0.4          P-14  13700                                              S-9     0.8          P-14  6200                                               S-9     1.0          P-14  3500                                               S-9     2.0          P-14  1200                                         167   S-10    0.2          P-14  38200                                              S-10    0.4          P-14  20500                                              S-10    0.8          P-14  7300                                               S-10    1.0          P-14  5400                                               S-10    2.0          P-14  1950                                         168   S-12    0.2          P-14  13000                                              S-12    0.4          P-14  4300                                               S-12    0.8          P-14   975                                               S-12    1.0          P-14   950                                               S-12    2.0          P-14   660                                         169   S-8     0.0          P-16  52500                                              S-8     0.2          P-16  95000                                              S-8     0.4          P-16  92000                                              S-8     0.8          P-16  122000                                             S-8     1.0          P-16  125000                                             S-8     2.0          P-16  138000                                       170   PS-9    0.2          P-16  73500                                              PS-9    0.4          P-16  53000                                              PS-9    0.8          P-16  25000                                              PS-9    1.0          P-16  21000                                              PS-9    2.0          P-16  5400                                         171   S-10    0.2          P-16  52800                                              S-10    0.4          P-16  34500                                              S-10    0.8          P-16  5400                                               S-10    1.0          P-16  2925                                               S-10    2.0          P-16   775                                         172   S-13    0.2          P-16  45800                                              S-13    0.4          P-16  54000                                              S-13    0.8          P-16  50800                                              S-13    1.0          P-16  54500                                              S-13    2.0          P-16  63000                                        173   S-14    0.2          P-16  22700                                              S-14    0.4          P-16  2480                                               S-14    0.8          P-16   710                                               S-14    1.0          P-16   532                                               S-14    2.0          P-16   415                                         174   S-8     0.0          P-29   285                                               S-8     0.2          P-29   285                                               S-8     0.4          P-29   360                                               S-8     0.8          P-29   477                                               S-8     1.0          P-29   505                                               S-8     2.0          P-29   837                                         175   S-9     0.2          P-29   282                                               S-9     0.4          P-29   285                                               S-9     0.8          P-29   284                                               S-9     1.0          P-29   298                                               S-9     2.0          P-29   322                                         176   S-10    0.2          P-29   272                                               S-10    0.4          P-29   278                                               S-10    0.8          P-29   285                                               S-10    1.0          P-29   297                                               S-10    2.0          P-29   315                                         177   S-12    0.2          P-29   267                                               S-12    0.4          P-29   279                                               S-12    0.8          P-29   298                                               S-12    1.0          P-29   311                                               S-12    2.0          P-29   320                                         178   S-8     0.0          P-30  19500                                              S-8     0.2          P-30  79000                                              S-8     0.4          P-30  71200                                              S-8     0.8          P-30  81000                                              S-8     1.0          P-30  89500                                              S-8     2.0          P-30  175000                                       179   S-9     0.2          P-30  52000                                              S-9     0.4          P-30  35500                                              S-9     0.8          P-30  16500                                              S-9     1.0          P-30  15600                                              S-9     2.0          P-30  5620                                         180   S-10    0.2          P-30  47200                                              S-10    0.4          P-30  26300                                              S-10    0.8          P-30  20300                                              S-10    1.0          P-30  13400                                              S-10    2.0          P-30  4700                                         181   S-12    0.2          P-30  23000                                              S-12    0.4          P-30  6840                                               S-12    0.8          P-30  3125                                               S-12    1.0          P-30  1750                                               S-12    2.0          P-30  1225                                         182   S-8     0.0          P-46  24500                                              S-8     0.2          P-46  79000                                              S-8     0.4          P-46  75000                                              S-8     0.8          P-46  86000                                              S-8     1.0          P-46  95000                                              S-8     2.0          P-46  150000                                       183   S-9     0.2          P-46  40500                                              S-9     0.4          P-46  31000                                              S-9     0.8          P-46  15300                                              S-9     1.0          P-46  9400                                               S-9     2.0          P-46  2300                                         184   S-11    0.2          P-46  20000                                              S-11    0.4          P-46  7300                                               S-11    0.8          P-46  1350                                               S-11    1.0          P-46   900                                               S-11    2.0          P-46   380                                         185   S-13    0.2          P-46  63500                                              S-13    0.4          P-46  42000                                              S-13    0.8          P-46  23000                                              S-13    1.0          P-46  16000                                              S-13    2.0          P-46  4850                                         186   S-14    0.2          P-46  36000                                              S-14    0.4          P-46  25000                                              S-14    0.8          P-46  11000                                              S-14    1.0          P-46  9300                                               S-14    2.0          P-46  1900                                         187   S-16    0.2          P-46  19000                                              S-16    0.4          P-46  9300                                               S-16    0.8          P-46  1250                                               S-16    1.0          P-46   750                                               S-16    2.0          P-46   290                                         ______________________________________                                    

EXAMPLES 188-232 Co-Thickening with Surfactants

The degree of ethoxylation of a surfactant added to an associativepolymer solution influences the co-thickening effect. The results inTable N below show the co-thickening effect produced by the additionwith thorough mixing of certain surfactants identified in Table M belowin the amounts identified in Table N to a 0.3% (Examples 172-189), 0.5%(Examples 190-215) or 0.75% (Example 216) alkaline solution of an alkalisoluble thickener identified in Table N as measured with a BrookfieldViscometer at 6 rpm at pH=9.0. ##STR17## R₂ =hydrogen or a R₃ --O--CH₂-- residue.

                  TABLE M                                                         ______________________________________                                                                          Moles of                                    Surfactant                                                                            R.sub.1       R.sub.2 /R.sub.3                                                                          Ethoxylation                                ______________________________________                                        S-17    Nonylphenol   Hydrogen (R.sub.2)                                                                        4                                           S-18    Nonylphenol   Hydrogen (R.sub.2)                                                                        6                                           S-19    Nonylphenol   Hydrogen (R.sub.2)                                                                        7                                           S-20    Nonylphenol   Hydrogen (R.sub.2)                                                                        8                                           S-21    Nonylphenol   Hydrogen (R.sub.2)                                                                        9                                           S-22    Nonylphenol   Hydrogen (R.sub.2)                                                                        10                                          S-23    Nonylphenol   Hydrogen (R.sub.2)                                                                        15                                          S-24    Nonylphenol   Hydrogen (R.sub.2)                                                                        25                                          S-25    Nonylphenol   Hydrogen (R.sub.2)                                                                        40                                          S-26    Octylphenol   Hydrogen (R.sub.2)                                                                        1                                           S-27    Octylphenol   Hydrogen (R.sub.2)                                                                        3                                           S-28    Octylphenol   Hydrogen (R.sub.2)                                                                        5                                           S-29    Octylphenol   Hydrogen (R.sub.2)                                                                        7                                           S-30    Octylphenol   Hydrogen (R.sub.2)                                                                        9                                           S-31    Octylphenol   Hydrogen (R.sub.2)                                                                        12                                          S-32    Octylphenol   Hydrogen (R.sub.2)                                                                        16                                          S-33    C11-C15 Secondary                                                                           Hydrogen (R.sub.2)                                                                        5                                                   Alcohol                                                               S-34    C11-C15 Secondary                                                                           Hydrogen (R.sub.2)                                                                        9                                                   Alcohol                                                               ______________________________________                                    

                  TABLE N                                                         ______________________________________                                                                             Brookfield                                                 Surfactant         Viscosity                                Ex-               Concentration                                                                             Thick- (cps) @                                  ample Surfactant  (wt. %)     ener   pH = 9.0                                 ______________________________________                                        188   S-17        0.8         P-1     890                                     189   S-18        0.8         P-1     1340                                    190   S-19        0.8         P-1     630                                     191   S-20        0.8         P-1     205                                     192   S-21        0.8         P-1     143                                     193   S-22        0.8         P-1     113                                     194   S-23        0.8         P-1      85                                     195   S-24        0.8         P-1      57                                     196   S-25        0.8         P-1      68                                     197   S-17        0.8         P-3    17800                                    198   S-18        0.8         P-3    35800                                    199   S-19        0.8         P-3    21300                                    200   S-20        0.8         P-3     820                                     201   S-21        0.8         P-3     230                                     202   S-22        0.8         P-3     147                                     203   S-23        0.8         P-3     118                                     204   S-24        0.8         P-3      82                                     205   S-25        0.8         P-3      77                                     206   S-17        0.8          P-42  57000                                    207   S-18        0.8          P-42  134000                                   208   S-19        0.8          P-42  112000                                   209   S-21        0.8          P-42   2450                                    210   S-22        0.8          P-42   800                                     211   S-23        0.8          P-42   3250                                    212   S-26        0.8          P-42  43000                                    213   S-27        0.8          P-42  37000                                    214   S-28        0.8          P-42  71000                                    215   S-29        0.8          P-42   5800                                    216   S-30        0.8          P-42   375                                     217   S-31        0.8          P-42   650                                     218   S-32        0.8          P-42   2400                                    219   S-17        0.8          P-46  68000                                    220   S-18        0.8          P-46  13000                                    221   S-19        0.8          P-46  88000                                    222   S-21        0.8          P-46   2900                                    223   S-22        0.8          P-46   1400                                    224   S-23        0.8          P-46   2400                                    225   S-26        0.8          P-46  25000                                    226   S-27        0.8          P-46  38500                                    227   S-28        0.8          P-46  77000                                    228   S-29        0.8          P-46   7200                                    229   S-30        0.8          P-46   550                                     230   S-31        0.8          P-46   690                                     231   S-32        0.8          P-46   1775                                    232   Aerosol ® OT                                                                          0.0         P-4    50500                                          Aerosol ® OT                                                                          0.1         P-4    93500                                          Aerosol ® OT                                                                          0.2         P-4    42000                                          Aerosol ® OT                                                                          0.4         P-4    11200                                          Aerosol ® OT                                                                          0.8         P-4     3700                                          Aerosol ® OT                                                                          1.0         P-4     7200                                          Aerosol ® OT                                                                          2.0         P-4    10600                                    ______________________________________                                    

EXAMPLES 233-245 Co-Thickening with Solvents and Non-Solvents

Solvents and non-solvents added to an associative polymer solutioninfluences the co-thickening effect. The results in Table P below showthe co-thickening effect produced by the addition with thorough mixingof certain solvents and non-solvents identified in Table O below in theamounts identified in Table P to a 0.75% alkaline solution of an alkalisoluble thickener identified in Table P as measured with a BrookfieldViscometer at 6 rpm at pH=9.0.

                  TABLE O                                                         ______________________________________                                        Solvent                                                                       Designation       Solvent                                                     ______________________________________                                        O-1               mineral spirits                                             O-2               butanol                                                     O-3               Isobutanol                                                  O-4               Isopropanol                                                 O-5               2-Ethylhexanol                                              O-6               Butyl Carbitol                                              O-7               Butyl DiPropasol                                            O-8               Butyl Propasol                                              O-9               Propyl DiPropasol                                            O-10             Propyl Propasol                                              O-11             Methyl DiPropasol                                            O-12             Methyl Propasol                                             ______________________________________                                    

                  TABLE P                                                         ______________________________________                                                               Solvent                                                                              Solvent O-1                                                                           Brookfield                                                     Concen-                                                                              Concen- Viscosity                                      Thick-  Sol-    tration                                                                              tration (cps) @                                 Example                                                                              ener    vent    (wt. %)                                                                              (wt. %) pH = 9.0                                ______________________________________                                        233    P-3     O-6      5     0       29200                                          P-3     O-6     10     0        865                                           P-3     O-6     20     0        625                                           P-3     O-6     40     0        720                                           P-3     O-6      5     5       15400                                          P-3     O-6     10     5        1125                                          P-3     O-6     20     5        735                                           P-3     O-6     40     5        780                                           P-3     O-6      5     10      56500                                          P-3     O-6     10     10       1050                                          P-3     O-6     20     10       835                                           P-3     O-6     40     10       832                                           P-3     O-6      5     20      41500                                          P-3     O-6     10     20       1625                                   234    P-3     O-7      0     0       76000                                          P-3     O-7      5     0        2150                                          P-3     O-7     10     0        3700                                          P-3     O-7     20     0        2000                                          P-3     O-7      0     5       89000                                          P-3     O-7      5     5       88000                                          P-3     O-7     10     5       50000                                          P-3     O-7     20     5       46500                                          P-3     O-7      0     10      102400                                         P-3     O-7      5     10      122000                                         P-3     O-7     10     10      72000                                          P-3     O-7      0     20      113000                                         P-3     O-7      5     20      158000                                         P-3     O-7     10     20      138000                                  235    P-3     O-8      5     0        1925                                          P-3     O-8     10     0        1150                                          P-3     O-8     20     0        2000                                          P-3     O-8     40     0        6200                                   236    P-3     O-9      5     0       36000                                          P-3     O-9     10     0        1200                                          P-3     O-9     20     0        440                                           P-3     O-9     40     0        1375                                   237    P-3      O-10    5     0        1375                                          P-3      O-10   10     0       45500                                          P-3      O-10   20     0        625                                           P-3      O-10   40     0        510                                    238    P-3      O-11    5     0       36000                                          P-3      O-11   10     0       20500                                          P-3      O-11   20     0        4200                                          P-3      O-11   40     0        550                                    239    P-3      O-12    0     0       76000                                          P-3      O-12    5     0       45000                                          P-3      O-12   10     0       24500                                          P-3      O-12   20     0        5800                                          P-3      O-12   40     0        675                                           P-3      O-12    5     5       51500                                          P-3      O-12   10     5       28500                                          P-3      O-12   20     5        7100                                          P-3      O-12   40     5        810                                           P-3      O-12    5     10      61200                                          P-3      O-12   10     10      33500                                          P-3      O-12   20     10       6400                                          P-3      O-12   40     10       950                                           P-3      O-12    5     20      86800                                          P-3      O-12   10     20      40500                                          P-3      O-12   20     20       7100                                          P-3      O-12   40     20       1350                                   240     P-14   O-7      0     0       150000                                          P-14   O-7      5     0        1350                                           P-14   O-7     10     0        4500                                           P-14   O-7     20     0        7000                                           P-14   O-7      0     5       140000                                          P-14   O-7      5     5       120000                                          P-14   O-7     10     5       78000                                           P-14   O-7      0     5       140000                                          P-14   O-7      5     10      158000                                          P-14   O-7     10     10      124000                                          P-14   O-7      0     20      136000                                          P-14   O-7      5     20      152000                                          P-14   O-7     10     20      142000                                  241     P-3a   O-2      0     0       132600                                          P-3a   O-2      5     0       17300                                           P-3a   O-2     10     0        850                                            P-3a   O-2     20     0        1425                                           P-3a   O-2     40     0        4750                                           P-3a   O-2      0     5       140000                                          P-3a   O-2      5     5       67000                                           P-3a   O-2     10     5        2500                                           P-3a   O-2     20     5        3000                                           P-3a   O-2      0     10      134000                                          P-3a   O-2      5     10      33000                                           P-3a   O-2     10     10       4000                                           P-3a   O-2     20     10       4900                                           P-3a   O-2      0     20      144000                                          P-3a   O-2      5     20      49000                                           P-3a   O-2     10     20       8000                                   242     P-3a   O-3      5     0       28500                                           P-3a   O-3     10     0        880                                            P-3a   O-3     20     0        1425                                           P-3a   O-3     40     0        4600                                           P-3a   O-3      5     5       80000                                           P-3a   O-3     10     5        2950                                           P-3a   O-3     20     5        3200                                           P-3a   O-3     40     5        6200                                           P-3a   O-3      5     10      78000                                           P-3a   O-3     10     10       5200                                           P-3a   O-3     20     10       6400                                           P-3a   O-3      5     20      136000                                          P-3a   O-3     10     20      20500                                   243     P-3a   O-4      5     0       94000                                           P-3a   O-4     10     0       29000                                           P-3a   O-4     20     0        1050                                           P-3a   O-4     40     0        850                                            P-3a   O-4      5     5       107400                                          P-3a   O-4     10     5       39000                                           P-3a   O-4     20     5        1225                                           P-3a   O-4     40     5        900                                            P-3a   O-4      5     10      134000                                          P-3a   O-4     10     10      41000                                           P-3a   O-4     20     10       1350                                           P-3a   O-4     40     10       1050                                           P-3a   O-4      5     20      164000                                          P-3a   O-4     10     20      33000                                           P-3a   O-4     20     20       1825                                           P-3a   O-4     40     20       1350                                   244     P-3a   O-5      5     0       93500                                           P-3a   O-5     10     0       136000                                          P-3a   O-5     20     0       178000                                  245     P-3a   O-7      5     0        2700                                           P-3a   O-7     10     0        6100                                           P-3a   O-7     20     0       11900                                   ______________________________________                                    

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

We claim:
 1. A latex composition containing water anda water-solublepolymer which comprises hydrophobic segments, each segment containing atleast one hydrophobic group or complex hydrophobic group covalentlybonded to the polymer, wherein the polymer has an amount of complexhydrophobic groups sufficient to provide for enhanced thickening ofaqueous solutions containing the polymer when compared with a polymer ofessentially the same structure but which has only hydrophobic groupsother than complex hydrophobic groups, wherein said complex hydrophobicgroup is derived from a compound represented by the formula selectedfrom: ##STR18## wherein R₁ and R₂ are the same or different and arehydrogen or a substituted or unsubstituted monovalent hydrocarbonresidue, R₃ is a substituted or unsubstituted divalent or trivalenthydrocarbon residue, each R₄ is the same or different and is asubstituted or unsubstituted divalent hydrocarbon residue, each R₅ isthe same or different and is substituted or unsubstituted divalenthydrocarbon residue, R₆ is hydrogen, a substituted or unsubstitutedmonovalent hydrocarbon residue or an ionic substituent, a and b are thesame or different and are a value of 0 or 1, and x and y are the same ordifferent and are a value of 0 or greater; provided at least two of R₁,R₂, R₃, R₄, R₅ and R₆ are a hydrocarbon residue having greater than 2carbon atoms in the case of R₁, R₂, and R₆ or having greater than 2pendant carbon atoms in the case of R₃, R₄ and R₅ ; and ##STR19##wherein R₇ and R₈ are the same or different and are hydrogen or asubstituted or unsubstituted monovalent hydrocarbon residue, R₉ and R₁₂are the same or different and are a substituted or unsubstituteddivalent or trivalent hydrocarbon residue, each R₁₀ is the same ordifferent and is a substituted or unsubstituted divalent hydrocarbonresidue, each R₁₃ is the same or different and is a substituted orunsubstituted divalent hydrocarbon residue, R₁₁ and R₁₄ are the same ordifferent and are hydrogen, a substituted or unsubstituted monovalenthydrocarbon residue or an ionic substituent, R₁₅ is a substituted orunsubstituted divalent hydrocarbon residue, d and e are the same ordifferent and are a value of 0 or 1, and f and g are the same ordifferent and are a value of 0 or greater; provided at least two of R₇,R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are a hydrocarbon residue havinggreater than 2 carbon atoms in the case of R₇, R₈, R₁₁ and R₁₄ or havinggreater than 2 pendant carbon atoms in the case of R₉, R₁₀, R₁₂, R₁₃,and R₁₅.
 2. A thickened aqueous composition containing water andawater-soluble polymer which comprises hydrophobic segments, each segmentcontaining at least one hydrophobic group or complex hydrophobic groupcovalently bonded to the polymer, wherein the polymer has an amount ofcomplex hydrophobic groups sufficient to provide for enhanced thickeningof aqueous solutions containing the polymer when compared with a polymerof essentially the same structure but which has only hydrophobic groupsother than complex hydrophobic groups, wherein said complex hydrophobicgroup is derived from a compound represented by the formula selectedfrom: ##STR20## wherein R₁ and R₂ are the same or different and arehydrogen or a substituted or unsubstituted monovalent hydrocarbonresidue, R₃ is a substituted or unsubstituted divalent or trivalenthydrocarbon residue, each R₄ is the same or different and is asubstituted or unsubstituted divalent hydrocarbon residue, each R₅ isthe same or different and is a substituted or unsubstituted divalenthydrocarbon residue, R₆ is a hydrogen, a substituted or unsubstitutedmonovalent hydrocarbon residue or an ionic substituent, a and b are thesame or different and are a value of 0 or 1, and x and y are the same ordifferent and are a value of 0 or greater; provided at least two of R₁,R₂, R₃, R₄, R₅ and R₆ are a hydrocarbon residue having greater than 2carbon atoms in the case of R₁, R₂ and R₆ or having greater than 2pendant carbon atoms in the case of R₃, R₄ and R₅ ; and ##STR21##wherein R₇ and R₈ are the same or different and are hydrogen or asubstituted or unsubstituted monovalent hydrocarbon residue, R₉ and R₁₂are the same or different and are a substituted or unsubstituteddivalent or trivalent hydrocarbon residue, each R₁₀ is the same ordifferent and is a substituted or unsubstituted divalent hydrocarbonresidue, each R₁₃ is the same or different and is a substituted orunsubstituted divalent hydrocarbon residue, R₁₁ and R₁₄ are the same ordifferent and are hydrogen, a substituted or unsubstituted monovalenthydrocarbon residue or an ionic substituentm R₁₅ is a substituted orunsubstituted divalent hydrocarbon residue, d and e are the same ordifferent and are a value of 0 or 1, and f and g are the same ordifferent and are a value of 0 or greater; provided at least two of R₇,R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ are a hydrocarbon residuehaving greater than 2 carbon atoms in the case of R₇, R₈, R₁₁ and R₁₄ orhaving greater than 2 pendant carbon atoms in the case of R₉, R₁₀, R₁₂,R₁₃, and R₁₅.